CN104379680A

CN104379680A - Vinyl terminated polyethylene with long chain branching

Info

Publication number: CN104379680A
Application number: CN201380031013.9A
Authority: CN
Inventors: G·R·吉斯布雷赫特; M·W·赫尔特卡普; M·科尔
Original assignee: Ramot at Tel Aviv University Ltd; Exxon Chemical Patents Inc
Current assignee: Ramot at Tel Aviv University Ltd; ExxonMobil Chemical Patents Inc
Priority date: 2012-08-03
Filing date: 2013-06-19
Publication date: 2015-02-25
Anticipated expiration: 2033-06-19
Also published as: EP2880097B1; EP2880097A1; CN104379680B; US9464148B2; US20140039140A1; US20150337058A1; EP2880097A4; US9045568B2; WO2014022012A1

Abstract

Vinyl terminated polyolefins with long chain branching produced with Salan catalysts having carbazole moieties.

Description

There is the polyolefine of the ethenyl blocking of long chain branching

Related application:

This application claims right of priority and the rights and interests of the provisional application US 61/679,579 that on August 3rd, 2012 submits to.

Invention field

The present invention relates to the ethene polymers of ethenyl blocking and/or there is the polymkeric substance of the long chain branching prepared by the new catalytic immunomodulator compounds comprising Salan ligand.

Background of invention

Olefin polymerization catalysis has very large purposes in the industry.Therefore there is interest and find that the commercial applications of new increase catalyzer also can produce the catalyst system of the polymkeric substance of the character with improvement.

Need new catalyzer with improving and catalyst system new for the polyolefine improved to obtain in this area, polymerization process etc.Therefore, the new of olefinic polymerization and the catalyst system improved is needed in this area, to realize specific polymer property, such as high polymers fusing point, high polymers molecular weight, long chain branching, ethenyl blocking, to increase being incorporated to of transformation efficiency or comonomer, and/or change the distribution of comonomer, and the character of the polymkeric substance of not deteriorated generation.

Summary of the invention

Present disclosure relates to catalyst compound, comprises the catalyst system of this compound, the preparation method of this catalyst compound and system, and the method for the olefinic polymerization of this catalyst compound of use and system.

In one embodiment, a kind of method comprises:

Contacted with catalyst system by one or more alkene under being enough to produce polyolefinic temperature, pressure and time, described polyolefine comprises:

A) at least 50% allyl chain ends; With

B) by ¹the Mn of at least 200g/mol that H NMR measures;

Described catalyst system comprises activator and the catalyst compound according to formula I, formula II or their combination:

Formula I is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each X is monovalence C independently ₁-C ₂₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or X ¹and X ²be joined together to form C ₄-C ₆₂the ring structure of ring-type or many rings, but condition is, the then X when M is trivalent ²do not exist;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ²⁸two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, or their combination; With

Y is divalence C ₁-C ₂₀alkyl;

Formula II is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ²¹in two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination; Condition is R ¹⁹not the carbazyl of carbazole or replacement, and

Y is divalence C ₁-C ₂₀alkyl.

In one embodiment, polyolefin polymer comprises:

A) at least 50% allyl chain ends; With

B) by ¹the Mn of at least 200g/mol that H NMR measures;

This polymkeric substance is prepared by comprising following method:

Under being enough to produce polyolefinic temperature, pressure and time, one or more alkene are contacted with catalyst system,

Formula I is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or two or more R ¹-R ²⁸c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, or their combination; With

Y is divalence C ₁-C ₂₀alkyl;

Formula II is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Y is divalence C ₁-C ₂₀alkyl.

Describe in detail

In order to the object of the present invention and claims, the new numbering plan of the periodic table of elements is as Chem.Eng.News, and 1985,63,27 use.Therefore, " group-4 metal " is the element of this periodic table of elements the 4th race.

In all structures described in the present specification and claims, solid line represents key, and arrow represents that key can be optional position, and each represented by dotted arrows has the key of the valence state of various degree and the coordination of various degree.

Except as otherwise noted, use term " alkyl " in this article interchangeably, " hydrocarbyl group " and " hydrocarbyl group ".In order to the object of present disclosure, alkyl is restricted in a suitable case (aromatic series or non-aromatic) can be the C of straight chain, side chain or ring-type ₁-C ₇₀base, or C ₁-C ₂₀base, or C ₁-C ₁₀base, or C ₆-C ₇₀base, or C ₆-C ₂₀base, or C ₇-C ₂₀base; With comprise by other alkyl and/or comprise one or more periodic table of elements 13-17 race element functional group replace alkyl.In addition, two or more this alkyl can form fused ring system together, comprise the fused ring system of the partially or completely hydrogenation that can comprise heterocyclic radical.

In order to object herein, the carbazyl of carbazole or replacement is expressed from the next:

Wherein each R ¹-R ⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ⁸in two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination.

Term " replacement " refers to that hydrogen atom in foundation structure and/or carbon atom are by alkyl, and/or functional group, and/or heteroatoms or replace containing heteroatomic group.Therefore, term alkyl comprises containing heteroatomic group.In order to object herein, heteroatoms is restricted to arbitrary atom in addition to carbon and hydrogen.Such as, methyl cyclopentadiene (Cp) is the Cp group (based on it structure) replaced by methyl (it also can be referred to as methyl functional group), ethanol is served as reasons the ethyl (based on it structure) that-OH functional group replaces, and pyridine is the phenyl in the foundation structure of the phenyl ring replaced by nitrogen-atoms with carbon.

In order to object herein, alkyl can independently selected from that replace or unsubstituted methyl, ethyl, vinyl, and following various isomer: propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, dodecyl, hentriacontyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, octadecylene base, 19 thiazolinyls, laurylene base, two hendecene bases, docosene base, tricosene base, two tetradecene bases, pentacosa alkene base, cerotene base, 27 thiazolinyls, two octadecylene bases, 29 thiazolinyls, 30 thiazolinyls, proyl, butynyl, pentynyl, hexin base, heptyne base, octyne base, n-heptylacetylene base, decynyl, undecyne base, dodecyne base, tridecyne base, 14 alkynyls, 15 alkynyls, hexadecyne base, 17 alkynyls, octadecyne base, 19 alkynyls, dodecyne base, two undecyne bases, two dodecyne bases, two tridecyne bases, 24 alkynyls, 25 alkynyls, two hexadecyne bases, 27 alkynyls, two octadecyne bases, 29 alkynyls, with 30 alkynyls.

In order to object herein, hydrocarbyl group also can comprise the isomer of saturated, part unsaturation and aromatic cyclic structure, and wherein above-described replacement type can additionally occur group.Term " aryl ", " aromatic yl group ", and/or " aryl " refers to aromatic cyclic structure, it can be replaced by hydrocarbyl group as defined herein and/or functional group.The example of aromatic yl group comprises: acenaphthenyl, acenaphthylenyl, acridyl, anthryl, benzo anthryl, benzimidazolyl-, benzoisoxazole base, benzofluoranthrene base, benzofuryl, benzo perylene base (benzoperylenyls), benzo pyrenyl, benzothiazolyl, aisaa benzothiophenyl, benzoxazolyl, benzyl, carbazyl, carbolinyl (carbolinyl), chrysenyl, cinnolines base, coronenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, dibenzo anthryl, fluoranthene base, fluorenyl, furyl, imidazolyl, indazolyl, indeno pyrenyl, indyl, indolinyl, isobenzofuran-base, pseudoindoyl, isoquinolyl (isoquinolinyl), isoxazolyl, methyl-benzyl, aminomethyl phenyl, naphthyl, oxazolyl, phenanthryl, phenyl, purine radicals, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridyl, pyrimidyl, pyrryl, quinazolyl, quinolonyl (quinolonyl), quinoxalinyl, thiazolyl, thiophenyl etc.

It should be understood that in order to object herein, when group is listed, it represent this group (types of radicals) and more than the generation of this group the foundation structure of other groups all that formed when limiting the replacement of type.The alkyl listed, thiazolinyl and alkynyl comprise all isomer, and it comprises cyclic isomers in a suitable case, such as, butyl comprises normal-butyl, 2-methyl-propyl, 1-methyl-propyl, the tertiary butyl, and cyclobutyl (with the cyclopropyl of similar replacement); Amyl group comprises n-pentyl, cyclopentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl, and neo-pentyl (with cyclobutyl and the cyclopropyl of similar replacement); Butenyl comprises 1-butylene base, crotyl, 3-butenyl, 1-methyl-1-propylene base, 1-methyl-2-propenyl, 2-methyl-1-propylene base, and the E of 2-methyl-2-propenyl (with cyclobutene base and cyclopropenyl radical) and Z-type.Ring compound has the form that substituting group comprises all isomer, and such as, aminomethyl phenyl comprises o-aminomethyl phenyl, m-aminomethyl phenyl and p-aminomethyl phenyl; 3,5-dimethylphenyl comprises 2,3-3,5-dimethylphenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-diphenyl methyl, 3,4-3,5-dimethylphenyl, and 3,5-3,5-dimethylphenyl.

Similarly, except as otherwise noted, term " functional group ", " group " and " substituting group " is also used in this article interchangeably.In order to object herein, functional group comprise organic and inorganic group or containing element periodictable the 13rd, 14,15,16, the part of the element of 17 races.Suitable functional group can comprise alkyl, such as, and alkyl, thiazolinyl, aryl, and/or halogen (Cl, Br, I, F), O, S, Se, Te, NR* _x, OR*, SeR*, TeR*, PR* _x, AsR* _x, SbR* _x, SR*, BR* _x, SiR* _x, GeR* _x, SnR* _x, PbR* _x, and/or etc., wherein R is above limited C ₁-C ₂₀alkyl and wherein x are for suitable integer is to provide electroneutral part.Other example of functional group comprises and is typically called as amine, imide, acid amides, ether, alcohol (oxyhydroxide), sulfonium ion, sulfate radical, phosphonium ion, halogen ion, phosphonate radical, alkanol, ester, carboxylate radical, those of aldehyde etc.

In order to object herein, " alkene (olefin) " is alternatively called as " alkene (alkene) ", is comprise carbon and hydrogen and have the straight chain of at least one double bond, side chain or ring compound.In order to the object of this specification sheets and its claims, when polymkeric substance or multipolymer be called as comprise alkene time, the alkene being present in this polymkeric substance or multipolymer is the alkene of polymeric species.Such as, when multipolymer is described to " ethene " content with 35wt%-55wt%, the link units that it should be understood that in multipolymer derives from ethene in polyreaction and the described unit obtained to be existed with 35wt%-55wt% based on the weighing scale of described multipolymer.

In order to object herein, " polymkeric substance " has two or more identical or different " chain link " unit." homopolymer " is the polymkeric substance with identical link units." multipolymer " is the polymkeric substance with two or more link units different separately." trimer " is the polymkeric substance with three kinds of respective different link units.Expression link units about " difference " of link units has at least one atom difference or different isomer each other.Therefore, the definition of multipolymer used herein comprises trimer etc.Oligopolymer typically is has low-molecular-weight polymkeric substance, such as, lower than the Mn of 25,000g/mol, or in one embodiment lower than 2,500g/mol, or the link units of low number, such as 75 link units or less." ethene polymers " or " ethylene copolymer " polymkeric substance deriving from the unit of ethene or multipolymer for comprising at least 50 % by mole, " propene polymer " or " propylene copolymer " for comprising polymkeric substance or the multipolymer that at least 50 % by mole derive from the unit of propylene, and by that analogy.

In order to the object of present disclosure, term " alpha-olefin " comprises C ₂-C ₂₂alkene.The nonrestrictive example of alpha-olefin comprises ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hendecene 1-laurylene, 1-tridecylene, 1-tetradecylene, 1-ten pentaene, 1-hexadecylene, 1-17 alkene, 1-octadecylene, 1-19 alkene, 1-icosa alkene, 1-bis-hendecene, 1-docosene, 1-tricosene, 1-bis-tetradecene, 1-pentacosa alkene, 1-cerotene, 1-27 alkene, 1-bis-octadecylene, 1-29 alkene, 1-30 alkene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 5-methyl isophthalic acid-nonene, 3, 5, 5-trimethylammonium-1-hexene, vinyl cyclohexane, with vinyl norbornene alkane.Cycloolefin and the nonrestrictive example of diolefine comprise cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, suberene, cyclooctene, cyclonoene, cyclodecene, norbornylene, 4-methyinorbornene, 2-methyl cyclopentene, 4-methyl cyclopentene, vinyl cyclohexane, norbornadiene, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene, vinyl cyclohexene, 5-vinyl-2-norbornylene, 1, 3-divinyl pentamethylene, 1, 2-divinylcyclohexane, 1, 3-divinylcyclohexane, 1, 4-divinylcyclohexane, 1, 5-divinyl cyclooctane, 1-allyl group-4-vinyl cyclohexane, 1, 4-diallyl hexanaphthene, 1-allyl group-5-VCO, with 1, 5-diallyl cyclooctane.

Term " catalyzer ", " catalyst compound " and " transistion metal compound " are restricted to that refer under suitable conditions can the compound of initiated polymerization catalysis.In explanation herein, described catalyzer can be described to catalyst precursor, procatalyst compound, or transistion metal compound, and uses these terms interchangeably.Catalyst compound can itself to make for causing catalysis or making for causing catalysis with activator combination.When catalyst compound and activator combination cause catalysis, catalyst compound is commonly called procatalyst or catalyst precursor." catalyst system " is the combination of at least one catalyst compound, at least one activator, optional coactivator and optional carrier, and monomer polymerization can be become polymkeric substance by wherein said system.In order to the object of the present invention and claims, when catalyst system is described to the component comprising neutral stable form, the ionic species understanding component is well to produce the form of polymkeric substance with monomer reaction by those of ordinary skill in the art.

In order to object herein, term " catalyst production " is the time period of T hour, uses the polymerizing catalyst comprising Wg catalyzer (cat) to produce measuring of polymkeric substance (P) of how many grams; Express by following formula: P/ (TxW) and with gPgcat ^-1hr ^-1unit express.Transformation efficiency is the amount of the monomer being converted into polymer product, and is recorded as mol% and calculates with the gauge of the monomer being fed to reactor based on the productive rate of polymkeric substance.Catalyst activity is that catalyst activity has how strong measuring and the quality (kgP/molcat) of resulting polymer (P) that produces of the every mol catalyst (cat) being recorded as use.

" anion ligand " is for being with one or more pairs of electronics to the part with the negative electricity of metal ion." neutral donor ligand " is to the part with the neutral charge of metal ion by one or more pairs of electronics.

Scavenging agent is typically added by removal of contamination to promote compound that is oligomeric or polymerization.Some scavenging agents also can serve as activator and can be referred to as coactivator.Not that the coactivator of scavenging agent also can use to form active catalyst together with activator.In one embodiment, coactivator can with catalyst compound pre-mixing to form alkylation catalyst compound.

Propene polymer is the polymkeric substance of the propylene with at least 50mol%.Except as otherwise noted, Mn used herein be by proton nuclear magnetic resonance spectroscopy ( ¹h NMR) number-average molecular weight that measures, Mw is the weight-average molecular weight measured by gel permeation chromatography (GPC), and Mz is the z average molecular weight measured by GPC, and wt% is weight percentage, and mol% is molar percentage.Molecular weight distribution (MWD) is defined as Mw divided by Mn.Unless otherwise noted, all molecular weight units, such as, Mw, Mn, Mz are g/mol.

Be right in this explanation and can use following abbreviation: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl group, iPr is sec.-propyl, n-Pr is n-propyl, Bu is butyl, iso-butyl is isobutyl-, the second month in a season-butyl is sec-butyl, tert-butyl is the tertiary butyl, n-butyl is normal-butyl, pMe is p-methyl, Bz is benzyl, THF is tetrahydrofuran (THF), Mes is mesitylene methyl, be also referred to as 1, 3, 5-Three methyl Benzene, Tol is toluene, TMS is TMS, TIBAL is triisobutyl aluminium, TNOAL is triisobutyl octyl aluminum, MAO is methylaluminoxane, be methoxymethoxy (being also referred to as methoxymethyl ether) with MOMO.

In order to object herein, except as otherwise noted, RT is restricted to the room temperature of 25 DEG C.Except as otherwise noted, all per-cent is weight percentage (wt%).

In explanation herein, Salan catalyzer can be described to catalyst precursor, procatalyst compound, Salan catalyst compound or transistion metal compound, and uses these terms interchangeably.

catalyst compound

In one embodiment, catalyzer comprises the disubstituted compound by the 3rd, 4,5 and/or 6 races of tetradentate two negatively charged ion Salan ligand load, can be used for olefin polymerization and/or alpha-olefin to produce polyolefine and/or poly-(alpha-olefin).In one embodiment, this catalyst compound is by following representation:

Wherein each solid line represents that covalent linkage and each represented by dotted arrows have the key of the valence state of various degree and the coordination of various degree;

M is the transition metal of the 3rd, 4,5 or 6 races covalently bonded to each Sauerstoffatom, and receives each nitrogen-atoms N with the valence state of various degree and coordinate bond ¹and N ²;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or two or more R ¹-R ²⁸c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination; With

Y is covalently bonded to nitrogen-atoms N ¹and N ²both and the bivalent hydrocarbon radical of bridging between which.In one embodiment, two or more R ¹-R ²⁸c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings.

In one embodiment, catalyst compound is expressed from the next:

Wherein A is expressed from the next, and is connected on carbazole ring and is labeled as N ³nitrogen-atoms:

Wherein A ' is expressed from the next, and is connected on carbazole ring and is labeled as N ⁴nitrogen-atoms:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or two or more R ¹-R ²⁸c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination; With

Y with Z-shaped become divalence C ₁-C ₂₀alkyl.In one embodiment, Y and Z is identical.In one embodiment, Y and Z is different.

In one embodiment, M is group-4 metal, or M is Hf, Ti and/or Zr, or M is Hf or Zr.In one embodiment, each X ¹and X ²independently selected from the alkyl with 1-20 carbon atom, negative hydrogen ion, acid amides, has the alkanol of 1-20 carbon atom, sulfonium ion, phosphonium ion, halogen ion, amine, phosphine, ether, their combination.

In one embodiment, X ¹and X ²formed together and there is the member ring systems of 4-62 carbon atom or a part for condensed ring.

In one embodiment, each X ¹and X ²independently selected from containing halogen, there is the alkyl of 1-7 carbon atom, benzyl, or their combination.

In one embodiment, Y comprises the divalence C containing the part connecting base skeleton ₁-C ₄₀alkyl, described connection base skeleton is included in nitrogen-atoms N ¹and N ²between connect or 1-18 carbon atom of bridging.In one embodiment, Y is C ₁-C ₄₀alkyl comprises the part containing connecting base skeleton, and described connection base skeleton comprises and connects nitrogen-atoms N ¹and N ²1-18 carbon atom, wherein said alkyl comprises O, S, S (O), S (O) ₂, Si (R ^*) ₂, P (R ^*), N or N (R ^*), wherein each R ^*be C independently ₁-C ₁₈alkyl.In one embodiment, Y is selected from ethene (-CH ₂cH ₂-) and 1,2-cyclohexylidene, and/or derive from-the CH of propylene ₂cH ₂cH ₂-group.In one embodiment, Y is the-CH deriving from propylene ₂cH ₂cH ₂-.

In one embodiment, each X is halogen or C independently ₁-C ₇alkyl.

In one embodiment, each X is benzyl.In one embodiment, each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen, halogen or C independently ₁-C ₃₀alkyl or C ₁-C ₁₀alkyl.In one embodiment, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸in one or more be methyl, fluorine-based, or their combination.

In one embodiment, M is Zr; X ¹and X ²for benzyl; R ¹and R ¹⁴for methyl; R ²-R ¹³and R ¹⁵-R ²⁸for hydrogen; Be ethylidene (-CH with Y ₂cH ₂-).

In one embodiment, M is Zr; X ¹and X ²for benzyl; R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl; R ², R ³, R ⁵-R ¹³, R ¹⁵, R ¹⁶and R ¹⁸-R ²⁸for hydrogen; Be ethylidene (-CH with Y ₂cH ₂-),

In one embodiment, M is Zr; X ¹and X ²for benzyl; R ¹and R ¹⁴for methyl; R ⁴and R ¹⁷for fluoro (F) functional group; R ², R ³, R ⁵-R ¹³, R ¹⁵, R ¹⁶and R ¹⁸-R ²⁸for hydrogen; Be ethylidene (-CH with Y ₂cH ₂-).

In one embodiment, M is Zr; X ¹and X ²for benzyl; R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl; R ⁸, R ¹¹, R ²¹and R ²⁴for the tertiary butyl; R ², R ³, R ⁵, R ⁶, R ⁷, R ⁹, R ¹⁰, R ¹², R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ¹⁹, R ²⁰, R ²², R ²³, R ²⁵, R ²⁶, R ²⁷, and R ²⁸for hydrogen; Be ethylidene (-CH with Y ₂cH ₂-).

In one embodiment, M is Zr; X ¹and X ²for benzyl; R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl; R ⁸, R ¹¹, R ²¹and R ²⁴for sym-trimethylbenzene base; R ², R ³, R ⁵, R ⁶, R ⁷, R ⁹, R ¹⁰, R ¹², R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ¹⁹, R ²⁰, R ²², R ²³, R ²⁵, R ²⁶, R ²⁷, and R ²⁸for hydrogen; Be ethylidene (-CH with Y ₂cH ₂-).

In one embodiment, catalyzer comprises the disubstituted compound by the 3rd, 4,5 and/or 6 races of tetradentate two negatively charged ion Salan ligand load, can be used for olefin polymerization and/or alpha-olefin to produce polyolefine and/or poly-(alpha-olefin).In one embodiment, catalyst compound is by following representation:

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or two or more R ¹-R ²¹c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, condition is R ¹⁹it not the carbazyl of carbazole or replacement; With

Y is covalently bonded to nitrogen-atoms N ¹and N ²both and the bivalent hydrocarbon radical of bridging between which.In one embodiment, two or more R ¹-R ²¹c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings.

Therefore, present disclosure relates to asymmetric Salan catalyzer in one embodiment.Salan catalyzer disclosed herein containing elements of symmetry, does not have asymmetric or non-palindrome.Asymmetric refer to when by comprise carbazole or replacement carbazyl a kind of phenol substituting group with at R ¹⁹containing the carbazyl of carbazole or replacement, (that is, condition is R in position ¹⁹the carbazyl of carbazole or replacement) the substituting group of another phenol time, two kinds of phenol moieties of Salan compound are differently replaced, as the above results show.

In one embodiment, catalyst compound is by following representation

Wherein A is by the following representation be connected on carbazole nitrogen-atoms:

M is the transition metal of the 3rd, 4,5 or 6 races, and it is covalently bonded to each Sauerstoffatom, and receives each nitrogen-atoms N with the valence state of various degree and coordinate bond ¹and N ²;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or two or more R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, condition is R ¹⁹be different from A; With

Y with Z-shaped become covalently bonded to nitrogen-atoms N ¹and N ²both and the bivalent hydrocarbon radical of bridging between which.In one embodiment, Y and Z is identical.In one embodiment, Y is different from Z.In one embodiment, two or more R ¹-R ²¹c can be joined together to form independently ₄-C ₆₂ring-type or polycyclic ring structure.

In one embodiment, M is group-4 metal, or M is Hf, Ti and/or Zr, or M is Hf or Zr.In one embodiment, each X ¹and X ²independently selected from having the alkyl of 1-20 carbon atom, negative hydrogen ion, acid amides, the alkanol with 1-20 carbon atom, sulfonium ion, phosphonium ion, halogen ion, amine, phosphine, ether and their combination.

In one embodiment, each X ¹and X ²independently selected from containing halogenation base, there is the alkyl of 1-7 carbon atom, benzyl, or their combination.

In one embodiment, Y comprises the divalence C containing the part connecting base skeleton ₁-C ₄₀alkyl, described connection base skeleton is included in nitrogen-atoms N ¹and N ²between connect or 1-18 carbon atom of bridging.In one embodiment, Y comprises the C containing the part connecting base skeleton ₁-C ₄₀alkyl, described connection base skeleton comprises and connects nitrogen-atoms N ¹and N ²1-18 carbon atom, wherein said alkyl comprises O, S, S (O), S (O) ₂, Si (R ^*) ₂, P (R ^*), N or N (R ^*), wherein each R ^*be C independently ₁-C ₁₈alkyl.In one embodiment, Y is selected from ethylidene (-CH ₂cH ₂-) and 1,2-cyclohexylidene, and/or derive from-the CH of propylene ₂cH ₂cH ₂-group.In one embodiment, Y is the-CH deriving from propylene ₂cH ₂cH ₂-.

In one embodiment, each X is halogen or C independently ₁-C ₇alkyl.

In one embodiment, each X is benzyl.In one embodiment, each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹be hydrogen independently, halogen, or C ₁-C ₃₀alkyl, or C ₁-C ₁₀alkyl, condition is R ¹⁹it not the carbazyl of carbazole or replacement.In one embodiment, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹in one or more be methyl, bromine, adamantyl, or their combination.

In one embodiment, M is Zr; X ¹and X ²for benzyl; R ¹and R ¹⁴for methyl; R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen; R ¹⁷and R ¹⁹for bromine; Be-CH with Y ₂cH ₂-.

In embodiments, M is Zr; X ¹and X ²for benzyl; R ¹, R ¹⁴and R ¹⁷for methyl; R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen; R ¹⁹for 1-adamantyl; Be-CH with Y ₂cH ₂-.

In one embodiment, M is Hf; X ¹and X ²for benzyl; R ¹and R ¹⁴for methyl; R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen; R ¹⁷for methyl; R ¹⁹for 1-adamantyl; Be-CH with Y ₂cH ₂-.

In one embodiment, two or more different catalyst compound are present in catalyst system as herein described.In one embodiment, two or more different catalyst compound are present in the reaction zone that method as herein described occurs wherein.When the catalyzer based on two kinds of transistion metal compounds is used for the catalyst system as mixing in a reactor, have selected two kinds of transistion metal compounds to make two kinds of catalyzer be compatible.Compatible catalyzer be have monomer and comonomer similar termination and insert kinetics and/or can not deleteriously with those catalyzer interact with each other.In order to object herein, the one or more catalyzer in below term " inconsistent catalyzer " refers to and meets:

1) activity of at least one catalyzer can be made those catalyzer being greater than 50% are reduced when existing together;

2) produce polymkeric substance under identical reaction conditions, be greater than those catalyzer of the molecular weight of the twice of the molecular weight of another kind of polymkeric substance to make a kind of polymkeric substance have; With

3) at identical conditions, comonomer be incorporated to or reactive ratio difference more than about 30% those catalyzer.Simple sieve method known to persons of ordinary skill in the art (is such as passed through ¹h or ¹³c NMR) can be used to determine which transistion metal compound is compatible.In one embodiment, catalyst system uses identical activator for catalyst compound.In one embodiment, use two or more various activators, such as non-coordinating anion activator and aikyiaiurnirsoxan beta capable of being combined.If it is not the X of negative hydrogen ion or alkyl that one or more catalyst compound contain ¹or X ²part, so in one embodiment, before interpolation non-coordinating anion activator, contacts aikyiaiurnirsoxan beta with catalyst compound.

In one embodiment, when employing two kinds transistion metal compound (procatalyst), they can use with any ratio.In one embodiment, First Transition metallic compound (A) drops within following scope with the mol ratio of Second Transition compound (B): (A:B) 1:1000-1000:1, or 1:100-500:1, or 1:10-200:1, or 1:1-100:1, or 1:1-75:1, or 5:1-50:1.The specific ratio selected depends on the procatalyst of the reality of selection, activation method, and the final product expected.In one embodiment, when use two kinds of procatalysts, when both activating with identical activator, available molar percentage counts 10:90-0.1:99 based on the total mole number of described procatalyst, or 25:75-99:1, or 50:50-99.5:0.5, or 50:50-99:1, or 75:25-99:1, or 90:10-99:1.

the method of Kaolinite Preparation of Catalyst compound

In embodiments, by transistion metal compound that two kinds of general synthesis path preparations are symmetrical.By a step Mannich reaction from parent phenol (reaction A) if or employ salicylic aldehyde and prepare parent salan part by two step imines-condensation/alkylation steps (reaction B).Then, be metal dibenzyl catalyst precursor by reacting ligand transformations with metal four-aryl parent material (such as, tetrabenzyl), to generate final title complex (reaction C).

Synthesis path by multi step format prepares asymmetric transistion metal compound.Then NaBH is passed through by the reaction of salicylic aldehyde and diamines ₄parent salan part is prepared in reduction.Then unsymmetric ligand (reaction D) is formed by the HBr elimination reaction of brooethyl phenol.Then, be metal dibenzyl catalyst precursor by reacting this ligand transformations with metal tetrabenzyl parent material, to generate final title complex (reaction E).

activator

Term " promotor " and " activator " be employed interchangeably to describe activator and the catalyst compound positively charged ion be restricted to by neutral catalyst compound being converted into catalytic activity to activate any compound of above-described arbitrary catalyst compound.Nonrestrictive activator, such as, comprises aikyiaiurnirsoxan beta, aluminum alkyls, Ionizing activators (it can be neutral or ion), and routine-type promotor.Activator can comprise aluminium alkoxide compound, the aluminium alkoxide compound of modification, with separating reaction, the metal ligand of σ-bonding is to make metal complex cationsization and to provide the non-coordinated of charge balance or the ionizing anionic precursors compound of weakly coordinating anion.

In one embodiment, alumoxane activator is used as the activator in catalyst composition.Aikyiaiurnirsoxan beta is normally containing-Al (R ¹) oligomeric compound of-O-subunit, wherein R ¹for alkyl.The example of aikyiaiurnirsoxan beta comprises methylaluminoxane (MAO), the methylaluminoxane (MMAO) of modification, ethylaluminoxane and isobutyl aluminium alkoxide.The aikyiaiurnirsoxan beta of alkylaluminoxane and modification is suitable for makes catalyst activator, particularly when catalyst precursor compounds comprises separable part (it is alkyl, halogen ion, alkanol or acid amides).Also the mixture of the aikyiaiurnirsoxan beta of different aikyiaiurnirsoxan beta and modification can be used.In one embodiment, the methylaluminoxane of visual clarification can be used.The aikyiaiurnirsoxan beta can filtering muddiness or gel is to produce clear soln or can pour out the aikyiaiurnirsoxan beta of clarification from the solution of muddiness.Available aikyiaiurnirsoxan beta is that the methylaluminoxane (MMAO) of modification is described in U.S. Patent number 5,041,584 and/or be purchased from AkzoChemicals, Inc. with trade name 3A type modified methylaluminoxane.Also solid aikyiaiurnirsoxan beta can be used.

When activator is aikyiaiurnirsoxan beta (modification or unmodified), in one embodiment, the maximum of activator at 5000 times of molar excess Al/M relative to catalyst compound (every metal catalytic site).In one embodiment, according to the compound of the minimum activator catalysis agent ratio that the volumetric molar concentration of transition metal M calculates, be the mole number of the aluminum ratio transition metal M of 1 mole or less in one embodiment.In one embodiment, activator comprises aikyiaiurnirsoxan beta, and aikyiaiurnirsoxan beta exists with the ratio of the mole number of catalyst compound with the aluminium of 1 mole or more.In one embodiment, minimum activator and catalyst compound mol ratio are 1:1 mol ratio.Other embodiment of the scope of Al:M comprises 1:1-500:1, or 1:1-200:1, or 1:1-100:1, or 1:1-50:1.

In one embodiment, few or do not have aikyiaiurnirsoxan beta (that is, being less than 0.001wt%) to be used in polymerization process as herein described.In one embodiment, aikyiaiurnirsoxan beta is with 0.00 % by mole of existence, or aikyiaiurnirsoxan beta is to be less than 500:1, or is less than 300:1, or is less than 100:1, or the mol ratio of the aluminium and catalyst compound transition metal that are less than 1:1 exists.

Term " non-coordinating anion " (NCA) refers to not coordinating to positively charged ion, or only weak coordinating to cationic negatively charged ion, keeps sufficiently unstable to be replaced by neutral Lewis base thus." compatible " non-coordinating anion is not degraded to neutral those.Further, anion substituent or fragment can not be transferred to positively charged ion to make it form neutral transition metal compound and the neutral by-product from negatively charged ion by negatively charged ion.According to the present invention can non-coordinating anion be be polymerized or catalyst system compatible, make transition-metal cation pass through to balance its ionic charge for+1 and stabilization, and still sufficiently unstable those to make to be replaced between polymerization period.

In one embodiment, ionization or stoichiometric activator can be used, it can be neutral or ionization, such as three (normal-butyl) ammonium boron metalloid precursor, many halos are mixed borine (heteroborane) negatively charged ion (WO 98/43983), boric acid (U.S. Patent number 5,942,, or their combination 459).In one embodiment, neutrality or ion activation agent can be used in combination separately or with the alumoxane activator of aikyiaiurnirsoxan beta or modification.

The example of the activator of neutral stoichiometric comprises trisubstituted boron, tellurium, aluminium, gallium, and indium, or their mixture.Three substituting groups or group can be identical or different, and in one embodiment, are selected from replacement or unsubstituted alkyl independently of one another, thiazolinyl, alkynyl, aryl, alkoxyl group, and halogen.In one embodiment, three group independent selected from halo, list or polycyclic (comprising halogen substiuted) aryl, alkyl, and alkenyl compound, and their mixture; Or independently selected from having the thiazolinyl of 1-20 carbon atom, there is the alkyl of 1-20 carbon atom, there is the alkoxyl group of 1-20 carbon atom and there is the aryl of 3-20 carbon atom or the aryl of replacement.In one embodiment, three substituting groups are the alkyl with 1-20 carbon atom, phenyl, naphthyl, or their mixture.In one embodiment, three groups are halogenated aryl, such as, and fluoro aryl.In one embodiment, the activator of neutral stoichiometric is three-perfluorophenyl boron or three-perfluoronapthyl boron.

In one embodiment, the activator compound of Ionic stoichiometric can comprise active proton, or some other positively charged ions, and they associate with the residual ion of ionic compound, but do not have coordination, or is only loosely coordination.Suitable example comprises the compound etc. be described in Publication about Document: open EP 0 570 982 A in Europe; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0 277 004 A; U.S. Patent number 5,153,157; 5,198,401; 5,066,741; 5,206,197; 5,241,025; 5,384,299; 5,502,124; With WO 1996/04319; All documents are all incorporated to herein by reference.

In one embodiment, compound as activator comprises positively charged ion (this positively charged ion is the Bronsted acid that such as can provide proton), with the compatible non-coordinating anion of relatively large (bulky), this negatively charged ion can be stabilized in these two kinds of compounds in conjunction with time formed active catalyst species (such as, 4th race's positively charged ion), and described negatively charged ion will be sufficiently unstable with by olefinic, diolefinic or acetylene series unsaturated materials or the such as replacement such as ether, amine of other neutral Lewis base.Two classes can compatible non-coordinating anion be disclosed in EP 0 277,003 A1, and EP 0 277,004 A1, it comprises anion binding title complex, comprise multiple lipophilic group covalently coordinating to and the charged metal in shielding center or metalloid core; Multiple boron atoms such as carborane is comprised, metallocarborane, and borine with negatively charged ion,

In one embodiment, stoichiometric activator comprises positively charged ion and anionic group, and can be represented by following formula (1):

(Z) _d ⁺(A ^d-) (1)

Wherein Z is (L-H) or reducible Lewis acid, and L is neutral Lewis base; H is hydrogen; (L-H)+be Bronsted acid; A ^d-for having the non-coordinating anion of electric charge d-; Be the integer of 1-3 with d.

When Z is (L-H) for (L-H) to make cationic components _d ⁺time, described cationic components can comprise the protonated Lewis base that Bronsted acid such as can make a Partial protons, such as, from the alkyl or aryl of catalyst precursor, produces cationic transition metal material, or the positively charged ion (L-H) of activation _d ⁺for Bronsted acid, proton can be given and catalyst precursor, produce transition-metal cation, comprise ammonium ion, oxygen, phosphorus, silicon, with their mixture, or methylamine, aniline, dimethyl amine, diethylamide, methylphenylamine, diphenylamine, Trimethylamine, triethylamine, N, accelerine, methyldiphenyl base amine, pyridine, to bromine N, accelerine, to nitro-N, ammonium in accelerine, triethyl phosphine, triphenylphosphine, with the phosphorus in diphenylphosphine, ether (such as dimethyl ether Anaesthetie Ether), tetrahydrofuran (THF), oxygen in He diox, sulfonium in thioether (such as diethyl thioether) and tetramethylene sulfide, with their mixture.

When Z is reducible Lewis acid, it can by formula: (Ar ₃c ⁺) represent, wherein Ar is the aryl of aryl or hybrid atom MCM-41, or C ₁-C ₄₀alkyl, described reducible Lewis acid can by formula: (Ph ₃c ⁺) represent, wherein Ph is the phenyl of phenyl or hybrid atom MCM-41, and/or C ₁-C ₄₀alkyl.In one embodiment, reducible Lewis acid is triphenylcarbenium.

Anionic group A ^d-embodiment comprise there is formula [M ^k+q _n] ^d-those, wherein k is 1,2, or 3; N is 1,2,3,4,5 or 6, or 3,4,5 or 6; N-k=d; M is selected from the element in the periodic table of elements the 13rd race or boron or aluminium, be negative hydrogen ion independently with Q, the dialkyl amide base of bridging or non-bridging, halogen ion, alkanol, aromatic oxide, alkyl, described Q has 20 carbon atoms at the most, and restricted condition is Q is halogen ion in no more than appearance place, and two Q groups can form ring structure.Each Q can fluoridize alkyl for what have a 1-20 carbon atom, or each Q is fluoro aryl, or each Q is five fluorine-based aryl.Suitable A ^d-the example of component also comprises as U.S. Patent number 5, and 447, two boron compounds disclosed in 895, it is all incorporated to herein by reference.

In one embodiment, the present invention relates to the method for olefin polymerization, it comprises by alkene (such as, ethene) and Salan catalyst compound, chain-transfer agent (CTA) and the boracic NCA activating agent represented by formula (1), wherein: Z is (L-H) or reducible Lewis acid; L is neutral Lewis base (as further described above); H is hydrogen; (L-H) be Bronsted acid (as further described above); A ^d-for having electric charge d ^-boracic non-coordinating anion (as further described above); D is 1,2, or 3.

In one embodiment, in the arbitrary NCA represented by above-described formula 1, anionic group A ^d-by formula [M* ^k*+q* _n*] ^d*-represent, wherein k* is 1,2, or 3; N* is 1,2,3,4,5, or 6 (or 1,2,3, or 4); N*-k*=d*; M* is boron; With Q* independently selected from negative hydrogen ion, the dialkyl amide base of bridging or non-bridging, halogen, alkanol, aromatic oxide, alkyl, it is be halogen at no more than 1 appearance place Q* that described Q* has 20 carbon atom restricted conditions at the most.

The invention still further relates to the method for olefin polymerization, it comprises alkene (such as ethene) and Salan catalyst compound as above, optionally with CTA and the NCA activating agent represented by formula (2):

R _nM**(ArNHal) _4-n(2)

Wherein R is single anion ligand; M** is the 13rd race's metal or metalloid; ArNHal is halo, nitrogenous aromatic ring, Ppolynuclear aromatic ring, or aromatic ring set, and wherein two or more rings (or fused ring system) directly connect each other or together; Be 0,1,2 with n, or 3.Typically, the NCA of the negatively charged ion of contained 2 also comprises the suitable positively charged ion substantially not disturbing the ionic catalyst complexes formed by transistion metal compound, or positively charged ion is Z as above _d ⁺.

In one embodiment, in the anion-containing NCA of any bag represented by above-described formula 2, R is selected from C ₁-C ₃₀alkyl.In one embodiment, C ₁-C ₃₀alkyl can by one or more C ₁-C ₂₀alkyl, halogen ion, the organometalloid that alkyl replaces, dialkyl amide base, alkoxyl group, aryloxy, alkyl sulphur bridge (alkysulfido), aryl sulphur bridge (arylsulfido), alkyl phosphorus bridge (alkylphosphido), aryl phosphonium ion (arylphosphide), or other anion substituent replaces; Fluorion; Large volume alkanol, wherein large volume refers to C ₄-C ₂₀alkyl;--SR ¹,--NR ² ₂, and--PR ³ ₂, wherein each R ¹, R ², or R ³be C as defined above independently ₁-C ₃₀alkyl; Or C ₁-C ₃₀the organometalloid that alkyl replaces.

In one embodiment, in the anion-containing NCA of any bag represented by above-described formula 2, NCA also comprises positively charged ion, and described positively charged ion comprises by formula: (Ar ₃c ⁺) reducible Lewis acid of representing, wherein Ar is the aryl of aryl or hybrid atom MCM-41, and/or C ₁-C ₄₀alkyl, or reducible Lewis acid is by formula: (Ph ₃c ⁺) represent, wherein Ph is the phenyl of phenyl or one or more hybrid atom MCM-41, and/or C ₁-C ₄₀alkyl.

In one embodiment, in the anion-containing NCA of any bag represented by above-described formula 2, NCA also can comprise by formula (L-H) _d ⁺the positively charged ion represented, wherein L is neutral Lewis base; H is hydrogen; (L-H) be Bronsted acid; Be 1,2 with d, or 3, or (L-H) _d ⁺for Bronsted acid, it is selected from ammonium, oxygen, phosphorus, silicon and their mixture.

The further example of available activator comprises and is disclosed in U.S. Patent number 7,297,653 and 7,799,879 those, it is all incorporated to herein by reference.

In one embodiment, herein available activator comprises the salt of the cationic oxygenant that represented by formula (3) and non-coordinated, compatible negatively charged ion:

(OX ^e+) _d(A ^d-) _e(3)

Wherein OX ^e+for having the cationic oxygenant of electric charge e+; E is 1,2, or 3; D is 1,2 or 3; And A ^d-for having the non-coordinating anion (as further described above) of electric charge d-.The example of cationic oxygenant comprises: ferrocene salt, the ferrocene salt of alkyl-replacement, Ag ⁺, or Pb ^{+ 2}.A ^d-suitable embodiment comprise four (pentafluorophenyl group) borate.

In one embodiment, Salan catalyst compound as herein described, CTA, and/or NCA can use together with large volume activator." large volume activator " used herein refers to the anionic activator be expressed from the next:

Wherein each R ₁be halogen independently, or fluorine;

Each R ₂be halogen independently, C ₆-C ₂₀the aromatic hydrocarbyl replaced or formula-O-Si-R _asiloxy, wherein R _afor C ₁-C ₂₀alkyl or hy drocarbylsilyl (or R ₂for fluorine-based or perfluorinated phenyl group);

Each R ₃for halogen-containing, C ₆-C ₂₀the aromatic hydrocarbyl replaced or formula-O-Si-R _asiloxy, wherein R _afor C ₁-C ₂₀alkyl or hy drocarbylsilyl (or R ₃for fluorine or C ₆perfluorinated aromatic alkyl); Wherein R ₂and R ₃can form that one or more are saturated or unsaturated, replace or unsubstituted ring (or R ₂and R ₃form perfluorinated phenyl group ring);

L is neutral Lewis base; (L-H) ⁺for Bronsted acid; D is 1,2, or 3;

Wherein negatively charged ion has the molecular weight being greater than 1020g/mol; With

Three substituting groups wherein at least on B atom have separately and are greater than , or be greater than , or be greater than molecular volume.

" molecular volume " is used as the approximate number of the space multistory size of activator molecule in the solution herein.The substituent contrast of differing molecular volume makes to have and is considered to " volume is less " than having to compare compared with the substituting group of macromole volume compared with the substituting group of small molecules volume.On the contrary, there is the substituting group " volume is larger " that can be considered to than having compared with small molecules volume compared with the substituting group of macromole volume.

Can as " A Simple " Back of the Envelope " Method forEstimating the Densities and Molecular Volumes of Liquids andSolids; " Journal of Chemical Education, 71st volume, o.11, in November, 1994, in 962-964 page, report calculates molecular volume.Use formula: MV=8.3V _scalculating molecular volume (MV) (with for unit), wherein V _sfor the volume recorded.V _sbe the relative volume of the atom formed and, and use the relative volume of following table to be calculated by substituent molecular formula.For condensed ring, V _severy condensed ring reduces 7.5%.

Element	Relative volume
		H	1
First short period, Li-F	2
		Second short period, Na-Cl	4
First long period, K-Br	5
		Second long period, Rb-I	7.5
3rd long period, Cs-Bi	9

Be applicable to the bulky substituent of exemplary activator herein and their respective volumes recorded and molecular volume be shown in following table.Empty key table shows and is bonded to boron, as above general formula.

Exemplary large volume activator for this paper catalyst system comprises: four (perfluoronapthyl) boric acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid tripropyl ammonium, four (perfluoronapthyl) boric acid three (normal-butyl) ammonium, four (perfluoronapthyl) boric acid three (tertiary butyl) ammonium, four (perfluoronapthyl) boric acid N, accelerine salt, four (perfluoronapthyl) boric acid N, N-diethylbenzene amine salt, four (perfluoronapthyl) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (perfluoronapthyl) boric acid is tall and erect, four (perfluoronapthyl) triphenylcarbenium, four (perfluoronapthyl) boric acid triphenyl phosphorus, four (perfluoronapthyl) boric acid triethyl silicon, four (perfluoronapthyl) boric acid benzene (diazonium salt), four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) ammonium, four (perfluorinated biphenyl) boric acid three (tertiary butyl) ammonium, four (perfluorinated biphenyl) boric acid N, accelerine salt, four (perfluorinated biphenyl) boric acid N, N-diethylbenzene amine salt, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (perfluorinated biphenyl) boric acid is tall and erect, four (perfluorinated biphenyl) borate, four (perfluorinated biphenyl) boric acid triphenyl phosphorus, four (perfluorinated biphenyl) boric acid triethyl silicon, four (perfluorinated biphenyl) boric acid benzene (diazonium salt), [the 4-tertiary butyl-PhNMe ₂h] [(C ₆f ₃(C ₆f ₅) ₂) ₄b], and be disclosed in U.S. Patent number 7,297, the type of 653, it is all incorporated to herein by reference.

Exemplary, but be not restrictive, the example that can be used as the boron compound of activator according to present disclosure in method comprises:

Tetraphenylboronic acid trimethyl ammonium, tetraphenylboronic acid triethyl ammonium, tetraphenylboronic acid tripropyl ammonium, tetraphenylboronic acid three (normal-butyl) ammonium, tetraphenylboronic acid three (tertiary butyl) ammonium, tetraphenylboronic acid N, accelerine salt, tetraphenylboronic acid N, N-diethylbenzene amine salt, tetraphenylboronic acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), tetraphenylboronic acid is tall and erect, tetraphenylboronic acid triphenylcarbenium, triphenyl phosphorus tetraphenylboronic acid, tetraphenylboronic acid triethyl silicon, tetraphenylboronic acid benzene (diazonium salt), four (pentafluorophenyl group) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid three (second month in a season-butyl) ammonium, four (pentafluorophenyl group) boric acid N, accelerine salt, four (pentafluorophenyl group) boric acid N, N-diethylbenzene amine salt, four (pentafluorophenyl group) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (pentafluorophenyl group) boric acid is tall and erect, four (pentafluorophenyl group) borate, four (pentafluorophenyl group) boric acid triphenyl phosphorus, four (pentafluorophenyl group) boric acid triethyl silicon, four (pentafluorophenyl group) boric acid benzene (diazonium salt), four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid trimethyl ammonium, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid triethyl ammonium, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid tripropyl ammonium, four-(2, 3, 4, the fluoro-phenyl of 6-tetra-) boric acid three (normal-butyl) ammonium, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid dimethyl (tertiary butyl) ammonium, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid N, accelerine salt, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid N, N-diethylbenzene amine salt, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid Zhuo, four-(2, 3, 4, 6-tetrafluoro phenyl) borate, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid triphenyl phosphorus, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid triethyl silicon, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid benzene (diazonium salt), four (perfluoronapthyl) boric acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid tripropyl ammonium, four (perfluoronapthyl) boric acid three (normal-butyl) ammonium, four (perfluoronapthyl) boric acid three (tertiary butyl) ammonium, four (perfluoronapthyl) boric acid N, accelerine salt, four (perfluoronapthyl) boric acid N, N-diethylbenzene amine salt, four (perfluoronapthyl) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (perfluoronapthyl) boric acid is tall and erect, four (perfluoronapthyl) triphenylcarbenium, four (perfluoronapthyl) boric acid triphenyl phosphorus, four (perfluoronapthyl) boric acid triethyl silicon, four (perfluoronapthyl) boric acid benzene (diazonium salt), four (perfluorinated biphenyl) boric acid trimethyl ammonium, triethyl ammonium four (perfluorinated biphenyl) boric acid, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) ammonium, four (perfluorinated biphenyl) boric acid three (tertiary butyl) ammonium, four (perfluorinated biphenyl) boric acid N, accelerine salt, four (perfluorinated biphenyl) boric acid N, N-diethylbenzene amine salt, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (perfluorinated biphenyl) boric acid is tall and erect, four (perfluorinated biphenyl) borate, four (perfluorinated biphenyl) boric acid triphenyl phosphorus, four (perfluorinated biphenyl) boric acid triethyl silicon, four (perfluorinated biphenyl) boric acid benzene (diazonium salt), four (3, two (trifluoromethyl) phenyl of 5-) boric acid trimethyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triethyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid tripropyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid three (normal-butyl) ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid three (tertiary butyl) ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, accelerine salt, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-diethylbenzene amine salt, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (3, two (trifluoromethyl) phenyl of 5-) boric acid Zhuo, four (3, two (trifluoromethyl) phenyl of 5-) borate, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triphenyl phosphorus, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triethyl silicon, four (3, two (trifluoromethyl) phenyl of 5-) boric acid benzene (diazonium salt), with

Dialkyl ammonium salt, such as:

Four (pentafluorophenyl group) boric acid two-(sec.-propyl) ammonium, and

Four (pentafluorophenyl group) boric acid dicyclohexyl ammonium; With the microcosmic salt of other three-replacement, such as four (pentafluorophenyl group) boric acid three (o-tolyl) phosphorus, and four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl) phosphorus.

Suitable activator comprises:

Four (perfluoronapthyl) boric acid N, accelerine salt, four (perfluorinated biphenyl) boric acid N, accelerine salt, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, accelerine salt, four (perfluoronapthyl) triphenylcarbenium, four (perfluorinated biphenyl) borate, four (two (trifluoromethyl) phenyl of 3,5-) borate, four (perfluorophenyl) borate, [Ph ₃c ⁺] [B (C ₆f ₅) ₄ ^-], [Me ₃nH ⁺] [B (C ₆f ₅) ₄ ^-]; 1-(4-(three (pentafluorophenyl group) boric acid)-2,3,5,6-tetrafluoro phenyl) tetramethyleneimine; With four (pentafluorophenyl group) boric acid, 4-(three (pentafluorophenyl group) boric acid)-2,3,5,6-ptfe pyridines.

In one embodiment, activator comprises triaryl carbon (such as tetraphenylboronic acid triphenylcarbenium, four (pentafluorophenyl group) borate, four-(2,3,4,6-tetrafluoro phenyl) borate, four (perfluoronapthyl) triphenylcarbenium, four (perfluorinated biphenyl) borate, four (two (trifluoromethyl) phenyl of 3,5-) boric acid) triphenylcarbenium.

In one embodiment, activator comprises four (pentafluorophenyl group) boric ammonium, four (pentafluorophenyl group) boric acid N, N-dialkyl benzene amine salt, four (pentafluorophenyl group) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four-(2, 3, 4, 6-tetrafluoro phenyl) boric ammonium, four-(2, 3, 4, 6-tetrafluoro phenyl) boric acid N, N-dialkyl benzene amine salt, four (perfluoronapthyl) boric ammonium, four (perfluoronapthyl) boric acid N, N-dialkyl benzene amine salt, four (perfluorinated biphenyl) boric ammonium, four (perfluorinated biphenyl) boric acid N, N-dialkyl benzene amine salt, four (3, two (trifluoromethyl) phenyl of 5-) boric ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dialkyl benzene amine salt, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dialkyl group-(2, 4, 6-Three methyl Benzene amine salt), (wherein alkyl is methyl for one or more in four (pentafluorophenyl group) boric acid two-(sec.-propyl) ammonium, ethyl, propyl group, normal-butyl, sec-butyl, or the tertiary butyl).

In one embodiment, before or after being combined with catalyst compound and/or CTA and/or NCA, or with catalyst compound and/or CTA, and/or NCA mixing before, any activator as herein described can be mixed together.

In one embodiment, two kinds of NCA activators to can be used in polymerization and the mol ratio of a NCA activator and the 2nd NCA activator can be any ratio.In one embodiment, the mol ratio of NCA activator-the two NCA activator is 0.01:1-10,000:1, or 0.1:1-1000:1, or 1:1-100:1.

In one embodiment, the ratio of NCA activator and catalyzer is 1:1 mol ratio, or 0.1:1-100:1, or 0.5:1-200:1, or 1:1-500:1 or 1:1-1000:1.In one embodiment, the ratio of NCA activator and catalyzer is 0.5:1-10:1, or 1:1-5:1.

In one embodiment, catalyst compound can with the built up section of aikyiaiurnirsoxan beta and NCA (see such as, US 5,153,157, US 5,453,410, EP 0 573 120 B1, WO94/07928, and WO 95/14044, wherein discuss the use that aikyiaiurnirsoxan beta is combined with ionic activator, all documents are incorporated to herein by reference).

scavenging agent or coactivator

In one embodiment, catalyst system can comprise scavenging agent and/or coactivator further.The suitable aluminium alkyl or the organo-aluminium compound that can be used as scavenging agent or coactivator comprise, such as, and trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three-n-hexyl aluminium, three-octyl aluminum etc.Also the material of other oxytropism can be used, such as zinc ethyl.In one embodiment, scavenging agent and/or coactivator based on the weighing scale of described catalyst system to be less than 14wt%, or 0.1-10wt%, or 0.5-7wt% exists.

support of the catalyst

In one embodiment, catalyst system can comprise inert support.In one embodiment, carrier comprises porous support, such as, and talcum, and/or inorganic oxide.Other suitable carrier comprises zeolite, clay, organic clay, or other organic or inorganic carrier any etc., or their mixture.

In one embodiment, carrier is the inorganic oxide of levigate form.Suitable inorganic oxide material for catalyst system herein comprises the 2nd, 4,13, and 14 family metal oxides, such as silicon-dioxide, aluminum oxide, and their mixture.Can separately or and silicon-dioxide, and/or other inorganic oxide that aluminum oxide adopts jointly comprises magnesium oxide, titanium oxide, zirconium white, montmorillonite, phyllosilicate, and/or etc.Other suitable carrier comprises levigate functionalised polyolefin, such as levigate polyethylene.

In one embodiment, carrier can have scope and is about 700m for about 10- ²the surface-area of/g, scope is the average particle size particle size that about 0.1-is about that the pore volume of 4.0cc/g and scope are about 5-about 500 μm, or scope is about 500m for about 50- ²the carrier surface area of/g, about 0.5-is about the average particle size particle size of the pore volume of 3.5cc/g and about 10-about 200 μm.In one embodiment, the scope of most of carrier surface area is about 400m for about 100- ²/ g, pore volume is about 3.0cc/g for about 0.8-and average particle size particle size is about 5-about 100 μm.In one embodiment, the scope of the average cell size of carrier is , or 50-is about , or 75-is about .In one embodiment, carrier is high surface area, amorphous have be more than or equal to about 300m ²the surface-area of/gm, and/or 1.65cm ³the silicon-dioxide of the pore volume of/gm.Suitable silicon-dioxide is commercially available by the Davison Chemical Division of W.R.Grace and Company with trade(brand)name Davison 952 or Davison 955.In one embodiment, carrier can comprise Davison 948.

In one embodiment, carrier should be dry substantially, that is, be substantially free of the water of absorption.About 100 DEG C of-Yue 1000 DEG C, or at least about 400 DEG C, or 500 DEG C, or the temperature of 600 DEG C carries out the drying of carrier by heating or calcining.When carrier is silicon-dioxide, be heated at least 200 DEG C, or about 200 DEG C of-Yue 850 DEG C, or at least 600 DEG C, continue about 1 minute-Yue 100 hours, or about 12 hours-Yue 72 hours, or about 24 hours-Yue 60 hours.According to present disclosure, in one embodiment, the carrier of calcining must have at least some reactive hydroxyl (OH) group to produce load type catalyst system.

In one embodiment, the carrier of calcining and at least one are comprised at least one catalyst compound to contact with the polymerizing catalyst of activator.In one embodiment, there is the carrier of reactive surfaces group (typically being hydroxyl), in non-polar solvent slurried and produce slurry contact with the solution of activator with catalyst compound.In one embodiment, the slurry of carrier first with activating agent about 0.5 hour-Yue 24 hours, or about 2 hours-Yue 16 hours, or about 4 hours-Yue time period of 8 hours.Then, by the carrier/activating agent of the solution of catalyst compound and isolation.In one embodiment, original position produces load type catalyst system.In alternate embodiments, first the slurry of carrier contacts about 0.5 hour-Yue 24 hours with catalyst compound, or about 2 hours-Yue 16 hours, or about 4 hours-Yue time of 8 hours.Then, the slurry of supported catalyst immunomodulator compounds is contacted with activator solution.

In one embodiment, by catalyzer, the mixture of activator and carrier is heated to about 0 DEG C of-Yue 70 DEG C, or to about 23 DEG C of-Yue 60 DEG C, or to room temperature.Typically be about 0.5 hour-Yue duration of contact 24 hours, or about 2 hours-Yue 16 hours, or about 4 hours-Yue 8 hours.

Suitable non-polar solvent is the material that all reactants herein use wherein, that is, activator and catalyst compound are solvable at least partly and it is liquid at the reaction temperatures.Suitable non-polar solvent comprises alkane, such as iso-pentane, hexane, normal heptane, octane, nonane, and decane, but other materials many also can be adopted to comprise naphthenic hydrocarbon, such as hexanaphthene, aromatics, such as benzene, toluene, and ethylbenzene.

polymerization process

In one embodiment, as mentioned above, polymerization process comprises monomer (such as ethene and propylene), and optionally comonomer, and comprises the catalyst system of activator with at least one catalyst compound and contacts.In one embodiment, catalyst compound and activator can be merged with any order, and can merge before monomer contact.In one embodiment, catalyst compound and/or activator merge after monomer contacts with monomer.

Available monomer comprises replacement or unsubstituted C herein ₂-C ₄₀alhpa olefin, or C ₂-C ₂₀alhpa olefin, or C ₂-C ₁₂alhpa olefin, or ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, hendecene, laurylene and their isomer.In one embodiment of the invention, monomer comprises propylene and optional comonomer, and this comonomer comprises ethene or C ₄-C ₄₀alkene or C ₄-C ₂₀alkene or C ₆-C ₁₂one or more in alkene.C ₄-C ₄₀olefinic monomer can be straight chain, side chain, or ring-type.C ₄-C ₄₀cycloolefin can be nervous or non-anxiety, monocycle or many rings, and optionally comprise heteroatoms and/or one or more functional groups.In embodiments, monomer comprises ethene or ethene and comonomer and comprises one or more C ₃-C ₄₀alkene, or C ₄-C ₂₀alkene, or C ₆-C ₁₂alkene.C ₃-C ₄₀olefinic monomer can be straight chain, side chain, or ring-type.C ₃-C ₄₀cycloolefin can be nervous or non-anxiety, monocycle or many rings, and optionally comprise heteroatoms and/or one or more functional groups.

Exemplary C ₂-C ₄₀olefinic monomer and optional comonomer comprise ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, hendecene, laurylene, norbornylene, norbornadiene, Dicyclopentadiene (DCPD), cyclopentenes, suberene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, the derivative of their replacement, with their isomer, or hexene, heptene, octene, nonene, decene, laurylene, cyclooctene, 1, 5-cyclooctadiene, 1-hydroxyl-4-cyclooctene, 1-acetoxyl group-4-cyclooctene, 5-methyl cyclopentene, cyclopentenes, Dicyclopentadiene (DCPD), norbornylene, norbornadiene, with their respective homologues and derivative, or norbornylene, norbornadiene, and Dicyclopentadiene (DCPD).

In one embodiment, one or more diene based on the total weight of described composition with at the most 10 % by weight, or 0.00001-1.0 % by weight, or 0.002-0.5 % by weight, or 0.003-0.2 % by weight is present in the polymkeric substance herein produced.In one embodiment, by 500ppm or less, or 400ppm or less, or 300ppm or less diene are added into polymerization.In one embodiment, will at least 50ppm, or 100ppm or more, or the diene of 150ppm or more is added into polymerization.

Spendable diolefinic monomer of the present invention comprises any hydrocarbon structure, or C ₄-C ₃₀, have at least two unsaturated link(age)s, wherein at least two unsaturated link(age)s are easily selected catalyzer by Stereoselective or non-cubic and are incorporated to polymkeric substance.In one embodiment, diolefinic monomer can be selected from α, ω-diene monomers (i.e. two-vinyl monomer).Again or, diolefinic monomer is straight chain two-vinyl monomer, more or for containing those of 4-30 carbon atom.The example of diene comprises divinyl, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, 11 carbon diene, 12 carbon diene, oleatridecadiene, 14 carbon diene, 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-11 carbon diene, 1, 11-12 carbon diene, 1, 12-oleatridecadiene, 1, 13-14 carbon diene, with low molecular weight polybutadiene (Mw is lower than 1000g/mol).Cyclic diene comprises cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, Dicyclopentadiene (DCPD) or be with or without substituent diolefine at each ring position containing senior ring.

In one embodiment, wherein butylene is comonomer, and butylene source can for comprising the butene stream of the mixing of various butylene isomer.Expect preferably to consume 1-butylene monomer by polymerization process.The use of the butene stream of this mixing will provide economic benefit, because the stream of these mixing is normally from the waste streams of process for refining, such as, and C ₄raffinate stream, and therefore can 1-butylene significantly than pure cheap.

Polymerization process can carry out in any known mode in this area according to present disclosure.Any suspension known in the art can be used, homogeneous phase, body, solution, slurry, or gas phase polymerization process.These methods can with interval, semi-batch, or continuous print mode is carried out.Polymerization in homogeneous phase method and slurry process are applicable herein, and wherein polymerization in homogeneous phase method is restricted to wherein the product of at least 90wt% is solvable method in reaction medium.Body homogeneous process is applicable herein, and wherein bulk process is defined as wherein all monomer concentrations be fed in reactor is the method for 70 volume % or more.In one embodiment, solvent or thinner do not exist or are added in reaction medium, (except being used as the carrier of catalyst system or other additive on a small quantity, or the amount typically found together with monomer; Such as, the propane in propylene).In one embodiment, method is slurry process.Term as used herein " slurry phase polymerisation process " refers to and wherein have employed loaded catalyst and the polymerization process that is polymerized on supported catalyst particle of monomer.At least the polymer product deriving from loaded catalyst of 95wt% is in granular form as solid particulate (being insoluble to thinner).

Suitable diluent/solvent for being polymerized comprises non-coordinated, inert liq.Example comprises the hydrocarbon of straight chain and side chain, such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and their mixture; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and their mixture, such as can (Isopar ^tM) commercially available; Full halogenated hydrocarbon, such as perfluorination C _4-10alkane, chlorobenzene, and the aromatics of aromatic base and alkyl replacement, such as benzene, toluene, sym-trimethylbenzene, and dimethylbenzene.Suitable solvent also comprises the liquefied olefines that can serve as monomer or comonomer, and described liquefied olefines comprises ethene, propylene, 1-butylene, 1-hexene, 1-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and their mixture.In one embodiment, aliphatic hydrocarbon solvent is used as solvent, such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and their mixture; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and their mixture.In one embodiment, solvent is not aromatics, or aromatics based on the weighing scale of described solvent to be less than 1wt%, or be less than 0.5wt%, or be less than 0.0wt% and be present in solvent.

In one embodiment, be 60vol% solvent or less for the input concentration of the monomer that is polymerized and comonomer based on the entire volume of described feed steam, or 40vol% or less, or 20vol% or less.Or described in be aggregated in bulk process and carry out.

Polymerization can be carried out at the polyvinyl any temperature being suitable for acquisition expectation and/or pressure.Suitable temperature and/or pressure comprise scope for about 0 DEG C of-Yue 300 DEG C, or about 20 DEG C of-Yue 200 DEG C, or about 35 DEG C of-Yue 150 DEG C, or about 50 DEG C of-Yue 150 DEG C, or about 40 DEG C of-Yue 120 DEG C, or the temperature of about 45 DEG C of-Yue 80 DEG C; Be about 10MPa with in scope for about 0.35MPa-, or about 0.45MPa-is about 6MPa, or about 0.5MPa-is about the pressure of 4MPa.

In one embodiment, carrying out time of reaction is about 0.1 minute-Yue 24 hours, or 16 hours at the most, or scope is about 5-250 minute, or about 10-120 minute.

In one embodiment, hydrogen is at 0.001-50psig (0.007-345kPa), or 0.01-25psig (0.07-172kPa), or is present in polymerization reactor under the pressure component of 0.1-10psig (0.7-70kPa).

In one embodiment, the activity of catalyzer is at least 50g/mmol/ hour, or 500g/mmol/ hour or more, or 5000g/mmol/hr or more, or 50,000g/mmol/hr or more.In alternate embodiments, the transformation efficiency of olefinic monomer is at least 10%, based on polymer yield and the monomer weight entering reaction zone, or 20% or more, or 30% or more, or 50% or more, or 80% or more.

In one embodiment, polymerizing condition comprises following one or more: the temperature of 1) 0-300 DEG C (or 25-150 DEG C, or 40-120 DEG C, or 45-80 DEG C); 2) pressure of normal atmosphere-10MPa (or 0.35-10MPa, or 0.45-6MPa, or 0.5-4MPa); 3) aliphatic hydrocarbon solvent (such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and their mixture; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and their mixture; Or wherein aromatics based on the weighing scale of described solvent to be less than 1wt%, or be less than 0.5wt%, or 0wt% is present in solvent) existence; 4) catalyst system wherein used in polymerization comprises and is less than 0.5mol%, or the aikyiaiurnirsoxan beta of 0mol%, or aikyiaiurnirsoxan beta is to be less than 500:1, or is less than 300:1, or is less than 100:1, or the mol ratio of the aluminium and transition metal that are less than 1:1 exists; 5) be aggregated in a reaction zone and carry out; 6) productive rate of catalyst compound be at least 80,000g/mmol/hr (or at least 150,000g/mmol/hr, or at least 200,000g/mmol/hr, or at least 250,000g/mmol/hr, or at least 300,000g/mmol/hr); 7) there is not (such as, existing with zero mol%) or scavenging agent to be less than 100:1 in scavenging agent (such as trialkyl aluminium compound), or is less than 50:1, or is less than 15:1, or be less than 10:1; And/or the mol ratio of the scavenging agent of 8 and transition metal exists, optionally hydrogen is present in polymerization reactor with the pressure component of 0.007-345kPa (0.001-50psig) (or 0.07-172kPa (0.01-25psig), or 0.7-70kPa (0.1-10psig)).

In one embodiment, the catalyst system used in polymerization comprises no more than a kind of catalyst compound." reaction zone " (being also referred to as " polymeric area ") is the container that polymerization occurs, such as batch reactor.When using multiple reactor with the structure of serial or parallel connection, each reactor is considered to polymeric area separately.For the multi-step polymerization in batch reactor and flow reactor, each polymerization stage is considered to polymeric area separately.In one embodiment, be aggregated in a reaction zone and carry out.

polyolefin product

Present disclosure also relates to the composition of matter produced by method as herein described.

In one embodiment, method as herein described produces alfon or propylene copolymer, such as, have the propylene-ethylene of the Mw/Mn being greater than 1-4 (or being greater than 1-3) and/or propylene-alpha-olefin (or C ₃-C ₂₀) multipolymer (such as butene-hexene multipolymer or propylene-octene Copolymer).

Similarly, method of the present invention produces olefin polymer, or polyethylene and homopolymer polypropylene and multipolymer.In one embodiment, the polymkeric substance herein produced is the homopolymer of ethene or propylene, is ethene or one or more C with 0-25 % by mole (or 0.5-20 % by mole, or 1-15 % by mole, or 3-10 % by mole) ₃-C ₂₀olefin comonomer (or C ₃-C ₁₂alpha-olefin, or propylene, butylene, hexene, octene, decene, laurylene, or propylene, butylene, hexene, octene) multipolymer, or be propylene or there is 0-25 % by mole of (or 0.5-20 % by mole, or 1-15 % by mole, or 3-10 % by mole) one or more C ₂or C ₄-C ₂₀olefin comonomer (or ethene or C ₄-C ₁₂alpha-olefin, or ethene, butylene, hexene, octene, decene, laurylene, or ethene, butylene, hexene, octene) multipolymer.

In one embodiment, monomer is ethene and comonomer is hexene, or the hexene of 1-15 % by mole, or the hexene of 1-10 % by mole.

In one embodiment, the polymkeric substance herein produced has 5,000-1,000,000g/mol (such as, 25,000-750,000g/mol, or 50,000-500,000g/mol) Mw, and/or be greater than 1-40, or 1.2-20, or 1.3-10, or 1.4-5, or 1.5-4, or the Mw/Mn of 1.5-3.

In one embodiment, the polymkeric substance herein produced has the unimodal or multimodal molecular weight distribution measured by gel permeation chromatography (GPC)." unimodal " refers to that GPC trace has a peak or flex point." multimodal " refers to that GPC trace has at least two peaks or flex point.Flex point is the point of the sign modification (such as, from negative to positive or vice versa) of the second derivative of wherein curve.

Except as otherwise noted, Mw, Mn, MWD are measured by GPC, and it is described in US2006/0173123 24-25 page, [0334]-[0341] section.

In one embodiment, polymkeric substance can be straight chain type, it can be measured by elution fractionation, wherein non-linear polymkeric substance has the CDBI being less than 45%, and straight linear polyethylene type refers to the polyethylene with the CDBI being greater than 50%, mensuration CDBI as described in WO93/03093 (US5206075).In one embodiment, the polymkeric substance herein produced has 50% or larger, or 60% or larger, or the composition Distribution Breadth Index (CDBI) of 70% or larger.CDBI is measuring of the composition distribution of monomer in polymer chain and is announce WO 93/03093 by being described in PCT disclosed in 18 days February in 1993, especially the 7th and 8 hurdles and people such as Wild, J.Poly.Sci., Poly.Phys.Ed., volume 20,441 pages (1982) and U.S. Patent number 5, the step of 008,204 is measured, and comprises as mensuration CDBI, omit and have lower than 15, the fraction of the weight-average molecular weight (Mw) of 000.

Have 4.5 or the polymkeric substance of less Mw/Mn can comprise the long chain branching of conspicuous level.The mode that the polymer chain (being formed by specific termination reaction mechanism contacting element site catalyst) that long chain branching is understood to be terminal unsaturation is incorporated to be similar to monomer is incorporated to the result of other polymer chain.Side chain therefore it is believed that be in the structure linear and can with ¹³do not have peak can by specifically owing to the level of this long chain branch in C NMR wave spectrum.In one embodiment, comprise the long chain branching of significant quantity according to the polymkeric substance of present disclosure production, be restricted to and there is basis ¹³the ratio being greater than the long chain branching of every 1000 carbon atoms at least 7 carbon of 0.5 of C NMR spectroscopic measurement.In one embodiment, the long chain branching ratio with the side chain of every 1000 carbon atoms at least 7 carbon according to ¹³c NMR spectroscopic measurement is greater than 1, or is greater than 1.5, or is greater than 2.

In one embodiment, comprise the ethenyl blocking of significant quantity according to the polymkeric substance of present disclosure production, the ratio being restricted to per molecule vinyl is more than or equal to 0.2.In one embodiment, when according to J.American Chemical Soc., 114,1992,1025-1032 page, or the explanation that provides of their equivalent is when measuring, have according to the polymkeric substance of present disclosure and be more than or equal to 0.5, or 0.7, or 0.8, or 0.9, or the ratio of the per molecule vinyl of 0.95.

The present invention relates to the ethene polymers with ethenyl blocking and long chain branching, it is by the Catalyst Production of method disclosed herein and use in one embodiment.In one embodiment, method as herein described produces Alathon or ethylene copolymer, such as ethene-alpha-olefin (preferred C ₃-C ₂₀) multipolymer (such as ethylene-propylene copolymer, ethylene-hexene co-polymers or ethylene-octene copolymer) has:

A) at least 50%, or at least 60%, 70%, 80%, 90%, 95%, 98%, or the allyl chain ends of 99%; And/or

B) by ¹at least 200g/mol that H NMR measures, or 250g/mol-100,000g/mol, such as, or 200g/mol-75,000g/mol, such as, or 200g/mol-60,000g/mol, or 300g/mol-60,000g/mol, or 750g/mol-30,000g/mol) Mn; And/or

C) side chain of at least 0.5 has every 1000 carbon atoms 7 or more carbon atom, or 1.0 or more, or 1.25 or more, or 1.5 or more, or 1.75 or more, or 2.0 or more, or 0.5-5.0, or 1.0-4.0, or 1.5-3.0; And/or

D) 100 DEG C or higher, or 110 DEG C or higher, or 120 DEG C or higher Tm; And/or

E) 1:1-5:1, or 1:1-4:1, or the ratio of the methyl chain end of 1:1-3:1 (being also referred to as the saturated end of the chain herein) and allyl chain ends; And/or

F) by ¹at least 50wt% that H NMR measures, or at least 60wt%, or at least 70wt%, or at least 80wt%, or at least 90wt%, or at least polymkeric substance (it can be Alathon or the multipolymer) per molecule of 95wt% or every segment have a vinyl; And/or substantially there is not diene, or polymkeric substance comprises the diene being less than or equaling about 0.01wt%; And/or

G) polymkeric substance comprises the ethene of at least 50mol%, or at least 60mol%, or at least 70mol%, or at least 75mol%, or at least 80mol%, or at least 85mol%, or at least 90mol%, or at least 95mol%, or the ethene of 100mol% substantially; And/or

H) be greater than 1 to 4, or be greater than the Mw/Mn of 1 to 3.

In one embodiment, the polymkeric substance herein produced have by ICPES measure (inductively coupled plasma emmission spectrum) be less than 1400ppm, or be less than 1200ppm, or be less than 1000ppm, or be less than 500ppm, or be less than the aluminium of 100ppm, it is described in J.W.Olesik, " Inductively Coupled Plasma-Optical EmissionSpectroscopy " is in Encyclopedia of Materials Characterization, C.R.Brundle, C.A.Evans, and S.Wilson Jr., eds., Butterworth-Heinemann, Boston, Mass., 1992, 633-644 page, it is used as the object of the content in order to measure element in material herein, and/or in one embodiment, polymkeric substance have measured by above-described ICPES be less than 1400ppm or be less than 1200ppm, or be less than 1000ppm, or be less than 500ppm, or be less than the transition metal of the 3rd, 4,5 or 6 races of 100ppm, or the 4th group 4 transition metal, or Ti, Zr and/or Hf.

In embodiments of the present invention, according to the ethene polymers of present disclosure have measured by ICPES be less than 1400ppm, or be less than 1200ppm, or be less than 1000ppm, or be less than 500ppm, or be less than the hafnium of 100ppm.

In embodiments of the present invention, according to the ethene polymers of present disclosure have measured by ICPES be less than 1400ppm, or be less than 1200ppm, or be less than 1000ppm, or be less than 500ppm, or be less than the zirconium of 100ppm.

In one embodiment, the polymkeric substance (it can be ethene polymers) herein produced has and is greater than 0.95g/cc, or is greater than 0.955g/cc, or is greater than the density of 0.96g/cc.

In one embodiment, the ethene polymers herein produced has 0.9 or less, or 0.85 or less, or the branch index (g' of 0.80 or less _vis), wherein mensuration g' as described below _vis.

In order to object herein, three online detector (differential refractive index detectors (DRI) are furnished with by using, light scattering detector (LS), and viscometer) high volume exclusion chromatography (from Waters Corporation or Polymer Laboratories) measure Mw, the number of Mz carbon atom, the numerical value of g and g' _vis.The details of experiment, comprises detector calibration, to be described in: T.Sun, P.Brant, R.R.Chance, and W.W.Graessley, Macromolecules, the 34th volume, No. 19,6812-6820, (2001) and quoting wherein.Employ three Polymer Laboratories PLgel 10mm Mixed-B LS posts.Apparent velocity is 0.5cm ³/ min, and apparent volume injected is 300 μ L.In an oven containing the various transmission lines, post and the differential refractometer (DRI detector) that remain on 145 DEG C.By 6 grams of Yoshinox BHTs are dissolved in the Aldrich reagent grade 1,2,4 trichlorobenzene (TCB) of 4 liters for the preparation of the solvent of testing as antioxidant.Then, by 0.7 μm of glass prefilter with subsequently by 0.1 μm of Teflon metre filter TCB mixture.Then by the degassed TCB of online de-gassing vessel, Size Exclusion Chromatograph SEC is entered afterwards.By the polymkeric substance of drying is placed in Glass Containers, add the TCB of desired amount, then at 160 DEG C of heated mixt, and continuously stirring prepares polymers soln in about 2 hours.All amounts are measured in gravimetric analysis mode.For with mass/volume unit express polymer concentration TCB density room temperature for 1.463g/ml and at 145 DEG C for 1.324g/ml.Injection concentration is 0.75-2.0mg/ml, and low concentration is used to the sample of higher molecular weight.Before each sample of test, cleaning DRI detector and syringe.Then, the flow velocity in equipment is increased to 0.5ml/ minute, and makes DRI stablize 8-9 hour, then injects the first sample.1-1.5 hour before test sample, opens LS laser apparatus.The concentration c of each position in color atlas uses following equation by the DRI signal I deducting baseline _dRIcalculate:

c＝K _DRII _DRI/(dn/dc)

Wherein K _dRIfor the constant determined by calibration DRI, and the index increment that (dn/dc) is system.For at TCB and the λ=690nm of 145 DEG C, refractive index n=1.500.In order to the object of the present invention and its claim, (dn/dc)=0.104 of propene polymer, butene polymers be 0.098 and other be 0.1.The unit of the parameter of the SEC method in whole specification sheets is such: concentration is with g/cm ³represent, molecular weight represents with g/ mole, and limiting viscosity is for represent with dL/g.

LS detector is Wyatt Technology High Temperature mini-DAWN.The molecular weight M of each position in color atlas, exports by using the Zimm model analysis LS of static light scattering and measures (M.B.Huglin, Light Scattering, PolymerSolutions, Academic Press, 1971):

\frac{K_{o} c}{ΔR (θ)} = \frac{1}{MP (θ)} + 2 A_{2} c

Herein, Δ R (θ) is the excessive Rayleigh intensity recorded at scatteringangleθ place, and c analyzes the polymer concentration measured, A by DRI ₂for second virial coefficient is [for the purposes of the present invention, for A propene polymer ₂=0.0006, for butene polymers be 0.0015 and for being 0.001 other], for propene polymer (dn/dc)=0.104, for being 0.098 and for being 0.1 other butene polymers, P (θ) is the shape factor for single dispersing random coil, and K _ooptical constant for for system:

K_{o} = \frac{4 π^{2} n^{2} {(dn / dc)}^{2}}{λ^{4} N_{A}}

Wherein N _afor Avogadro's numerical value, and (dn/dc) is the index increment for system.For at TCB and the λ=690nm of 145 DEG C, refractive index n=1.500.

The viscometer of the high temperature Viscotek Corporation with four kapillaries configured with the Wheatstone bridge configuration of two pressure transmitters is used for measuring specific viscosity.Sensor measures a total pressure drop of crossing over detector, and another sensor measurement dividing potential drop between bridge both sides.Flow through the specific viscosity η of the solution of viscometer _scalculated by their output.Calculated by following equation in the limiting viscosity [η] of each position chromatographic:

η _s＝c[η]+0.3(c[η]) ²

Wherein c is concentration and is exported by DRI to measure.

Branch index (g' _vis) use the output of following SEC-DRI-LS-VIS method to calculate.The average intrinsic viscosity [η] of sample _avgcalculated by following formula:

{[η]}_{ang} = \frac{Σ c_{i} {[η]}_{i}}{Σ c_{i}}

Wherein color atlas thin slice (slice) i between limit of integration is added up.Branch index g' _visbe restricted to:

g^{'} vis = \frac{{[η]}_{avg}}{{kM}_{v}^{α}}

Wherein, in order to the object of the present invention and claim thereof, α=0.695 of linear ethylene polymer and k=0.000579, the α=0.705k=0.000262 of straight chain propene polymer, and α=0.695 of linear butenes polymkeric substance and k=0.000181.M _vfor the viscosity-average molecular weight based on the molecular weight measured by LS analysis.

Parameter " g " (also referred to as " g value ") is restricted to Rg ² _pm/ Rg ² _ls, wherein Rg _pmfor the turning radius of poly-macromonomer, Rg ² _lsfor the turning radius of linear criterion, and Rg _ls=K _sm ^0.58wherein K _sfor power law coefficient (straight linear polyethylene is 0.023, and linear polypropylene is 0.0171, and straight chain polybutene is 0.0145), and M is molecular weight as above, Rg _pm=K _tm ^{α s}.α _sfor poly-macromolecular size factor, K _tfor the power law coefficient of poly-macromonomer.For the guidance selecting the linear criterion with molecular weight and co-monomer content and mensuration k-factor and alpha index, see Macromolecules, 2001,34,6812-6820.

At 120 DEG C, in 10mm probe, use ¹hydrogen frequency is the Varian spectrometer of at least 400MHz, collects ¹³c NMR data.During whole acquisition time, adopt the pulse of 90 degree, for providing the digital resolution of 0.1-0.12Hz and the acquisition time adjusted, the pulse collection time of lag of at least 10 seconds, the uncoupling of continuous print broad band proton, uses frequency sweep square-wave frequency modulation, does not adopt gate.Use and provide obtain spectrogram the mean time of the level of the signal to noise ratio of the signal needed for fully measuring.Sample is dissolved in tetrachloroethane-d with the concentration of 10-15wt% ₂, be then inserted in spectrometer magnet.Before data analysis, by setting (-CH ₂-) _nthe chemical potential in-migration of signal (wherein n>6 to 29.9ppm) quotes spectrogram.Use the signal qualification end of the chain of following table display for quantification.Do not report normal-butyl and n-propyl, this is their abundance low (being less than 5%) of the end of the chain owing to showing relative to following table.

The end of the chain	¹³CNMR chemical shift
		P～i-Bu	23-5-25.5 and 25.8-26.3ppm
E～i-Bu	39.5-40.2ppm
		P ~ vinyl	41.5-43ppm
E ~ vinyl	33.9-34.4ppm

By sample dissolution in d ₂-sym.-tetrachloroethane, uses the spectrogram of the NMR spectrometer record of 100MHz (or higher) at 125 DEG C.Polymkeric substance resonance peak is with reference to mmmm=21.8ppm.Be included in PolymerConformation and Configuration (the Academic Press being described in F.A.Bovey by the calculating in NMR characterize polymers, New York 1969) and the Polymer Sequence Determination of J.Randall ¹³c-NMRMethod (Academic Press, New York, 1977).

" allyl chain ends and the ethidine end of the chain than " is defined as the ratio of the per-cent of allyl chain ends and the per-cent of the ethidine end of the chain.

" allyl chain ends and the vinylidene end of the chain than " is defined as the ratio of the per-cent of allyl chain ends and the per-cent of the vinylidene end of the chain.

Term " allyl chain ends " (being also referred to as " allyl type vinyl " or " allyl type vinyl ends ") is defined as at least one according to following formula (CH ₂=CH-CH ₂-polymkeric substance) polymkeric substance of end that represents:

Wherein M representation polymer chain.

Term " the ethidine end of the chain " is restricted to has at least one end by (CH ₃-C (=CH ₂)-CH ₂-polymkeric substance) polymkeric substance that represents.

Term " the vinylidene end of the chain " is restricted to has at least one end by (CH ₃-C=CH ₂-CH ₂-polymkeric substance) polymkeric substance that represents.

In one embodiment, at 120 DEG C, use deuterate tetrachloroethane as solvent, use ¹h NMR measure on 500MHz machine allyl chain ends amount and selected when by ¹³c NMR confirms.Reported the numerical value of document, the distribution of proton and carbon wherein mass spectrum uses pure perdeuterated tetrachloroethane and carbon spectrum to use common tetrachloroethane and perdeuterated tetrachloroethane 50:50 mixture; For the propylene oligomer of ethenyl blocking, at 100 DEG C, for proton at 300MHz and the 75.43MHz of all spectrum of BRUKER AM 300 spectrometer record operate under to(for) carbon, see J.American Chemical Soc., 114,1992,1025-1032 page.

The polymkeric substance of ethenyl blocking also typically has the saturated end of the chain, is also referred to as methyl termini.Comprising C ₄or in the polymerization of more senior monomer (or " higher alkene " monomer), the saturated end of the chain can be C ₄or more senior (or " higher alkene ") end of the chain, be shown below:

Wherein M representation polymer chain and n are the integer being selected from 4-40.When there is no ethene or propylene in polymerization, this is especially correct.At ethene/(C ₄or more senior monomer) in copolymerization, polymer chain can cause the growth of vinyl monomer, is produced as the saturated end of the chain of the ethyl end of the chain thus.Exist wherein in the polymerization of propylene, polymer chain can cause the growth of propylene monomer, produces the isobutyl-end of the chain thus." the isobutyl-end of the chain " is defined as end position or the end of polymkeric substance, as shown in the formula expression:

Wherein M representation polymer chain.The step measurements isobutyl-end of the chain according to WO 2009/155471.

According to following NMR method measure Mn ( ¹h NMR).Room temperature or 120 DEG C (in order to the object of claim, 120 DEG C should be used), in 5mm probe, use and there is 250MHz, 400MHz, or 500MHz ¹the Varian spectrometer (in order to the object of claim, employing the proton frequency of 400MHz) of H frequency is collected ¹h NMR data.Use the maximum pulse of 45 DEG C, the signal record data of 8 seconds recurrent intervals and average 120 transitions.Integral light spectrum signal, by being multiplied by 1000 and by the overall number of result divided by carbon with various group, calculates the quantity of the degree of unsaturation type relative to 1000 carbon.By by the sum of unsaturated materials divided by 14,000 calculates Mn, and it has the unit of g/mol.The chemical shift region of olefin type is restricted between following SPECTRAL REGION.

dsc (DSC)

Tc (T _c), melt temperature (or fusing point, T _m), second-order transition temperature (T _g) and melting heat (H _f) on the instrument be purchased (such as, TA instrument 2920DSC), use dsc (DSC) to measure.Typically, at room temperature, the molded polymer of 6-10mg or plasticizing polymerization thing seal and are written into instrument in aluminium dish.In 10 DEG C/min heating rate, obtain data by sample being heated to above melt temperature at least 30 DEG C (typically being 220 DEG C for polypropylene).Sample keeps at least 5 minutes at such a temperature to eliminate thermal history.Then, under the rate of cooling of 20 DEG C/min, sample is cooled to lower than Tc at least 50 DEG C (typically being-100 DEG C for polypropylene) from melting.Sample keeps at least 5 minutes at such a temperature, and finally to heat obtaining other melting data (the second heating) at 10 DEG C/min.Change according to standard step analysis heat absorption melting transition (the first and second heating) and exothermic crystallization.Except as otherwise noted, the melt temperature (Tm) of report is the peak value melt temperature from the second heating.For the polymkeric substance demonstrating multiple peak, melt temperature is defined as the peak value melt temperature from the fusing track relevant to maximum caloric receptivity thermal response (instead of at peak that top temperature occurs).Similarly, Tc is defined as the peak crystallization temperature from the relevant crystallization track of crystallization maximum caloric receptivity thermal response (instead of at peak that top temperature occurs).

DSC area under a curve is used to determine transition heat (melting heat H during melting _f, or heat of crystallization H during crystallization _c), it can be used to calculate degree of crystallinity (being also referred to as percent crystallinity).Percent crystallinity (X%) uses following formula to calculate: [area under a curve (representing with J/g)/H ° (representing with J/g)] * 100, and wherein H ° is the desirable melting heat of the perfect crystallization of the homopolymer of major monomeric compoent.The numerical value of these H ° derives from Polymer Handbook, 4th edition, published by JohnWiley and Sons, New York 1999, difference is, the numerical value of 290J/g is used for H ° (polyethylene), and the numerical value of 140J/g is used for H ° (polybutene), and the numerical value of 207J/g is used for H ° (polypropylene).

Above DSC step (except sample is cooled to-100 DEG C, keeping then being heated to outside 200 DEG C with 10 DEG C/min for 5 minutes) is used to measure melting heat (Hm).Hm is measured at the first melt, instead of the second melt.Hm sample should not must to be heated to eliminate thermal history aged at room temperature at least 48 hours.

ethylene content

The ethylene content in ethylene copolymer is measured, except minimum signal to noise ratio should be outside 10,000:1 by ASTM D 5017-96.Propylene content in propylene copolymer adopts Di Martino and Kelchermans, J.Appl.Polym.Sci. 56, the approach of the following methods 1 in 1781 (1995) is determined, and uses the Polymer of Zhang 45, the peak of the higher alkene comonomer in 2651 (2004) distributes.

Also can use by using gel permeation chromatography (GPC) method the high volume exclusion chromatography (SEC being furnished with differential refractive index detector (DRI), from Waters Corporation or Polymer Laboratories) measure Mn, Mw, and Mz.The particular content of experiment is described in: T.Sun, P.Brant, R.R.Chance, and W.W.Graessley, Macromolecules, the 34th volume, No. 19,6812-6820 page, (2001) and reference thereof.Employ three Polymer Laboratories PLgel 10mm Mixed-B posts.Minimum flow velocity is 0.5cm ³/ min and minimum volume injected are 300 μ L.In an oven containing the various transmission lines remaining on 135 DEG C, post and differential refractometer (DRI detector).By 6 grams of butylated hydroxytoluenes as antioxidant being dissolved in 1,2, the 4-trichlorobenzene (TCB) of 4 liters of Aldrich reagent grades the solvent come for the preparation of SEC experiment.Then TCB mixture is filtered by 0.7 μm of glass prefilter, subsequently by 0.1 μm of Teflon metre filter.Then carry out degassed with online de-gassing vessel to TCB, enter SEC afterwards.Polymers soln is prepared in the following manner: dry polymer is placed in Glass Containers, adds the TCB of desired amount, then at 160 ° of C heated mixt and continuous print stir about 2 hours.All amounts are measured in gravimetric analysis mode.For with mass/volume unit express polymer concentration TCB density room temperature for 1.463g/ml and at 135 DEG C for 1.324g/ml.Injection concentration is 1.0-2.0mg/mL, and low concentration is used to the sample of higher molecular weight.Before each sample of test, cleaning DRI detector and syringe.Then, the flow velocity in equipment is increased to 0.5ml/ minute, and makes DRI stablize 8-9 hour, then injects the first sample.The concentration c of each position in color atlas uses following equation by the DRI signal I deducting baseline _dRIcalculate:

c＝K _DRII _DRI/(dn/dc)

Wherein K _dRIfor the constant determined by calibration DRI, and the index increment that (dn/dc) is system.For at TCB and λ=690nm, n=1.500 of 135 DEG C.In order to the present invention and the object of its claim, for propene polymer and ethene polymers, (dn/dc)=0.104, other is 0.1.The unit of the parameter of the SEC method in whole specification sheets is such: concentration is with g/cm ³represent, molecular weight represents with g/ mole, and limiting viscosity is for represent with dL/g.

blend

In one embodiment, before formation film, moulded product or other goods, the polymkeric substance herein produced (or polyethylene or the polypropylene) polymkeric substance other with one or more is combined.Other available polymkeric substance comprises polyethylene, isotactic polyprophlene, height isotactic polyprophlene, syndiotactic polypropylene, propylene and ethene, and/or butylene, and/or the random copolymers of hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, acrylic copolymer, polymethylmethacrylate or any other pass through the polymerisable polymkeric substance of high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber(EPR) (EPR), sulfuration EPR, EPDM, segmented copolymer, styrene block copolymer, polymeric amide, polycarbonate, PET resin, crosslinked polyethylene, the multipolymer of ethene and vinyl alcohol (EVOH), the polymkeric substance such as polystyrene of aromatic monomer, polyester, polyacetal, poly(vinylidene fluoride), polyoxyethylene glycol, and/or polyisobutene.

In one embodiment, polymkeric substance (or polyethylene or polypropylene) is based on the weighing scale of the polymkeric substance in described blend, with 10-99wt%, or 20-95wt%, or at least 30-90wt%, or at least 40-90wt%, or at least 50-90wt%, or at least 60-90wt%, or at least 70-90wt% is present in above-mentioned blend.

By by polymkeric substance of the present invention and the above-described blend of one or more polymkeric substance (as above) mixture manufacturing, to be linked together preparation feedback device blend by reactors in series, or by using in identical reactor more than a kind of catalyzer to produce the many kinds of substance of polymkeric substance.Polymkeric substance can be mixed together or can mix in an extruder before being injected into forcing machine.

Blend can use conventional equipment and method to be formed, such as by dry blended independent component and melting mixing in mixing machine subsequently, or pass through blending ingredients in mixing machine together, such as, Banbury mixing machine, Haake mixing machine, Brabender Banbury mixer, or list or twin screw extruder, it can comprise compounding extrusion machine for the direct downstream of polymerization process and sidewall forcing machine stream, and it can be included in powder or the particle of the loading hopper blending resin of film forcing machine.Additionally, additive can comprise in the blend, in one or more components in the blend, and/or forms the product from blend, such as film, as desired.This additive is that this area is known, and can comprise, such as: filler; Antioxidant (such as, fortified phenol class, such as IRGANOX 1010 or IRGANOX 1076, purchased from Ciba-Geigy); Phosphorous acid salt (such as, purchased from the IRGAFOS 168 of Ciba-Geigy); Antiseized (anti-cling) additive; Tackifier, such as polybutene, terpine resin, aliphatics and aromatic hydrocarbon resin, basic metal and stearin, and the rosin of hydrogenation; Ultra-violet stabilizer; Thermo-stabilizer; Anti-hard caking agent; Releasing agent; Static inhibitor; Pigment; Tinting material; Dyestuff; Wax; Silicon-dioxide; Filler; Talcum etc.

film

In one embodiment, any aforesaid polymkeric substance, such as aforesaid polypropylene or its blend, can be used to various end-use applications.Application comprises, and such as, list or multilayer inflation, to extrude and/or shrink film.These films can be extruded by any amount known or coextrusion technology shaping, such as blowing vacuolar membrane processing technology, wherein said composition can be extruded by annular port mould in molten state, then the melt forming single shaft or diaxial orientation is expanded, be cooled to the film of tubulose, blowing afterwards, then it can axially cut and launch to form flat film.Film can be subsequently by disorientation, uniaxial orientation, or diaxial orientation is to identical or different degree.One or more layers of film can be to identical or different degree with horizontal and/or longitudinal direction orientation.Typically cold drawn or hot-drawn method is used to realize diaxial orientation.Use tenter apparatus or two bubble method and can diaxial orientation be realized and can occur before or after individual course is gathered.Such as, polyethylene layer can be extruded coating or be laminated to orientation polypropylene layer on or polyethylene and polypropylene can together be coextruded formation film, then orientation.Similarly, on the polyethylene that the polypropylene of orientation can be in turn laminated to orientation or the polyethylene of orientation can be coated on polypropylene, then optionally combining even can by further orientation.Typically, film is with at the most 15, or the ratio of 5-7 is at longitudinal direction (MD), and with at the most 15, or the ratio of 7-9 is in transverse direction (TD) orientation.But, in one embodiment film with identical degree in MD and TD direction orientation.

The thickness variable of film, depends on required application; But thickness is that the film of 1-50 μm is normally suitable.Film needed for encapsulation be generally 10-50 μm thick.The thickness of sealing ply typically is 0.2-50 μm.In film, sealing ply or sealing ply can be had can only to exist only in inner or outer surface with outside surface.

In one embodiment, one or more layers can pass through corona treatment, electron beam irradiation, gamma-radiation, flame treating or microwave modification.In one embodiment, by one deck in corona treatment modified surface layer or two-layer.

moulded parts

Composition as herein described (or polypropene composition) also with any molding methods for the preparation of moulded parts, can include but not limited to, injection moulding, gas assistant injection molding, extrusion and blow molding, injection blow molding is shaping, and injection stretch blow is shaping, compression molding, rotoforming, foaming, thermoforming, sheet material is extruded, and section bar extrusion.Moulding process is that those of ordinary skill in the art are known.

And composition as herein described (or polypropene composition) forms the end-use articles of expectation by any suitable mode known in the art.Thermoforming, vacuum formation, blow molding, rotoforming, solidifying molded, transfer molding, wet-process coating or contact moulding, cast molding, cold-forming matched-die molding, injection moulding, spraying technique, section bar coextrusion or their combination are the methods typically used.

Thermoforming is the method that the sheet plastic making at least one pliable and tough forms the shape expected.Typically, the extruded film (with other layer any or material) of composition of the present invention is placed in transmission frame during heating to be held up.Be introduced into by transmission frame in baking oven, it is pre-add hotting mask before shaping.Once heated film, transmission frame is led back shaping instrument.Then, film is evacuated on shaping instrument by vacuum to hold it in suitable position and to close shaping recruitment tool.Described instrument keeps cutting out to cool film and then described instrument is opened.Then, shaping laminated product is taken out from described instrument.Once the layer of material reaches hot-forming temperature, typically be 140 DEG C-185 DEG C or higher, realize thermoforming by vacuum, positive air pressure, auxiliary (plug-assisted) vacuum forming of plug or these combination and version.Employ the foam step of preliminary draft, particularly on large parts to improve the dispersion of material.

Blow molding is that it is shaping that it comprises injection blow molding, multi-layer blow molding for the suitable molding mode of the another kind of composition of the present invention, extrusion and blow molding, and stretch blow-molded, be specially adapted to object that is that substantially close or sky, such as, gas-holder and other fluid container.The more details of blow molding are described in, such as, Concise Encyclopedia of PolymerScience and Engineering 90-92 (Jacqueline I.Kroschwitz, ed., John Wiley & Sons 1990).

Similarly, the shaping geometrical shape of expectation and the Making mold moulded parts of thickness with being solidified into moulded parts of molten polymer can be made by being injected into by molten polymer.By extruding substantially flat section bar from punch die, can be expressed on cooling roller, or manufacture thin slice by calendering.Thin slice is considered to have the thickness of 254 μm-2540 μm (10 millimeters-100 millimeters) usually, but any given thin slice can be thicker significantly.

non-woven fabrics and fiber

Above-described polyolefin compositions also can any nonwoven fabric and fibre manufacture (include but not limited to, melt and blow method, spun-bond process, film perforate (film aperturing), and staple card) for the preparation of nonwoven fabric of the present invention and fiber.Also continuous print ultimate fibre technique can be used.Or use spunbond process.Spunbond process is that this area is known.Usual it comprises extrudes fiber by spinning nozzle.Then, these fibers use high-speed air stretch and be layered on endless belt.Then, pressure roller is normally used for heating net and fiber is bonded to one another, but also can use other technology, and such as ultrasonic bonds and tackiness agent bond.

Embodiment

Therefore, present disclosure relates to following embodiment:

A. a method, comprising:

A) allyl chain ends of at least 50%; With

B) by ¹the Mn of at least 200g/mol that H NMR measures;

Formula I is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each X is monovalence C independently ₁-C ₂₀hydrocarbyl group, the functional group of the element of containing element periodictable 13-17 race, or X ¹and X ²be joined together to form C ₄-C ₆₂the ring structure of ring-type or many rings, but condition is, the then X when M is trivalent ²do not exist;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀hydrocarbyl group, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ²⁸in two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination; With

Y is divalence C ₁-C ₂₀alkyl;

Formula II is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹be hydrogen independently, C ₁-C ₄₀hydrocarbyl group, the functional group of the element of containing element periodictable 13-17 race, or two or more R ¹-R ²¹c can be joined together to form independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination; The restricted condition be subject to is R ¹⁹not the carbazole group of carbazole or replacement, and

Y is divalence C ₁-C ₂₀hydrocarbyl group.

B. the method according to embodiment A, the R of its Chinese style I ¹-R ²⁸, the R of formula II ¹-R ²¹, or above-mentioned two or more in both are joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings.

C. the method according to any one of embodiment A-B, its Chinese style I, formula II, or more both M be Hf, Ti or Zr.

D. the method according to any one of embodiment A-C, its Chinese style I, formula II, or more both each X be halogen or C independently ₁-C ₇hydrocarbyl group.

E. the method according to any one of embodiment A-D, its Chinese style I, formula II, or more both each X be benzyl group.

F. the method according to any one of embodiment A-E, each R of its Chinese style (I) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸, each R of formula (II) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹, or more be both hydrogen, halogen or C independently ₁-C ₃₀hydrocarbyl group.

G. the method according to any one of embodiment A-F, each R of its Chinese style (I) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³r ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸, each R of formula (II) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹, or more be both hydrogen, halogen or C independently ₁-C ₁₀hydrocarbyl group.

H. the method according to any one of embodiment A-G, the R of its Chinese style I ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³r ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸in one or more be methyl group, fluorine-based or their combination.

I. the method according to any one of embodiment A-H, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹and R ¹⁴for methyl group;

R ²-R ¹³and R ¹⁵-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

J. the method according to any one of embodiment A-I, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl group;

R ², R ³, R ⁵-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

K. the method according to any one of embodiment A-J, wherein, catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹and R ¹⁴for methyl group;

R ⁴and R ¹⁷for fluorine-based;

R ², R ³, R ⁵-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

L. the method according to any one of embodiment A-K, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl group;

R ⁸, R ¹¹, R ²¹and R ²⁴for tertiary butyl groups;

R ², R ³, R ⁵, R ⁶, R ⁷, R ⁹, R ¹⁰, R ¹², R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ¹⁹, R ²⁰, R ²², R ²³, R ²⁵and R ²⁶-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

M. the method according to any one of embodiment A-L, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl group;

R ⁸, R ¹¹, R ²¹and R ²⁴for sym-trimethylbenzene base group;

Y is-CH ₂cH ₂-.

N. the method according to any one of embodiment A-M, the R of its Chinese style II ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹in one or more be methyl group, bromo, adamantyl group or their combination.

O. the method according to any one of embodiment A-N, wherein said catalyst compound according to formula II, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹and R ¹⁴for methyl group;

R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen;

R ¹⁷and R ¹⁹for bromine; With

Y is-CH ₂cH ₂-.

P. the method according to any one of embodiment A-O, wherein said catalyst compound according to formula II, wherein,

M is Zr;

X ¹and X ²for benzyl group;

R ¹, R ¹⁴and R ¹⁷for methyl group;

R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰, and R ²¹for hydrogen;

R ¹⁹for 1-adamantyl group; With

Y is-CH ₂cH ₂-.

Q. the method according to any one of embodiment A-P, wherein said catalyst compound according to formula II, wherein,

M is Hf;

X ¹and X ²for benzyl group;

R ¹and R ¹⁴and R ¹⁷for methyl group;

R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen;

R ¹⁹for 1-adamantyl group; With

Y is-CH ₂cH ₂-.

R. the method according to any one of embodiment A-Q, its Chinese style I, formula II, or more both Y be-CH ₂cH ₂-or 1,2-cyclohexylidene.

S. the method according to any one of embodiment A-R, its Chinese style I, formula II, or more both Y be-CH ₂cH ₂cH ₂-.

T. the method according to any one of embodiment A-S, its Chinese style I, formula II, or more both Y comprise the C connecting base skeleton ₁-C ₄₀bivalent hydrocarbon radical group, described connection base skeleton is included in nitrogen-atoms N ¹and N ²1-18 carbon atom of bridging before.

U. the method according to any one of embodiment A-T, its Chinese style I, formula II, or more both Y for comprising O, S, S (O), S (O) ₂, Si (R ') ₂, P (R '), N, N (R '), or the C of their combination ₁-C ₄₀bivalent hydrocarbon radical group, wherein each R ' is C independently ₁-C ₁₈hydrocarbyl group.

V. the method according to any one of embodiment A-U, wherein said activator comprises aikyiaiurnirsoxan beta, non-coordinating anion activator or their combination.

W. the method according to any one of embodiment A-V, wherein said activator comprises aikyiaiurnirsoxan beta and aikyiaiurnirsoxan beta exists with the ratio of the mole number of catalyst compound with the aluminium of 1 mole or more.

X. the method according to any one of embodiment A-W, wherein said activator is expressed from the next:

(Z) _d ⁺(A ^d-)

Wherein Z is (L-H), or reducible Lewis acid, and wherein L is neutral Lewis base;

H is hydrogen;

(L-H) ⁺for Bronsted acid;

There is the A of electric charge d- ^d-for non-coordinating anion; With

D is the integer of 1-3.

Y. the method according to any one of embodiment A-X, wherein said activator is expressed from the next:

(Z) _d ⁺(A ^d-)

Wherein A ^d-for non-coordinating anion has electric charge d-;

D is the integer of 1-3, and

Z is by formula: (Ar ₃c ⁺) reducible Lewis acid of representing, wherein Ar is aromatic yl group, by the aromatic yl group of hybrid atom MCM-41, by one or more C ₁-C ₄₀the aromatic yl group that hydrocarbyl group replaces, the aromatic yl group replaced by one or more functional groups of the element of containing element periodictable 13-17 race, or their combination.

Z. the method according to any one of embodiment A-Y, wherein said activator is selected from:

Four (pentafluorophenyl group) boric acid DMA salt, four (pentafluorophenyl group) borate, four (perfluoronapthyl) boric acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid tripropyl ammonium, four (perfluoronapthyl) boric acid three (normal-butyl) ammonium, four (perfluoronapthyl) boric acid three (tertiary butyl) ammonium, four (perfluoronapthyl) boric acid DMA salt, four (perfluoronapthyl) boric acid N, N-diethylbenzene amine salt, four (perfluoronapthyl) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline salt), four (perfluoronapthyl) boric acid is tall and erect, four (perfluoronapthyl) triphenylcarbenium, four (perfluoronapthyl) boric acid triphenyl phosphorus, four (perfluoronapthyl) boric acid triethyl coordination silicon salt, four (perfluoronapthyl) boric acid benzene (diazonium salt), four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) ammonium, four (perfluorinated biphenyl) boric acid three (tertiary butyl) ammonium, four (perfluorinated biphenyl) boric acid DMA salt, four (perfluorinated biphenyl) boric acid N, N-diethylbenzene amine salt, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline salt), four (perfluorinated biphenyl) boric acid is tall and erect, four (perfluorinated biphenyl) borate, four (perfluorinated biphenyl) boric acid triphenyl phosphorus, four (perfluorinated biphenyl) boric acid triethyl coordination silicon salt, four (perfluorinated biphenyl) boric acid benzene (diazonium salt), [the 4-tertiary butyl-PhNMe ₂h] [(C ₆f ₃(C ₆f ₅) ₂) ₄b], tetraphenylboronic acid trimethyl ammonium, tetraphenylboronic acid triethyl ammonium, tetraphenylboronic acid tripropyl ammonium, tetraphenylboronic acid three (normal-butyl) ammonium, tetraphenylboronic acid three (tertiary butyl) ammonium, tetraphenylboronic acid DMA salt, tetraphenylboronic acid N, N-diethylbenzene amine salt, tetraphenylboronic acid N, N-dimethyl-(2，4，6-trimethyl aniline salt), tetraphenylboronic acid is tall and erect, tetraphenylboronic acid triphenylcarbenium, tetraphenylboronic acid triphenyl phosphorus, tetraphenylboronic acid triethyl coordination silicon salt, tetraphenylboronic acid benzene (diazonium salt), four (pentafluorophenyl group) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid three (second month in a season-butyl) ammonium, four (pentafluorophenyl group) boric acid DMA salt four (pentafluorophenyl group) boric acid, N, N-diethylbenzene amine salt, four (pentafluorophenyl group) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline salt), four (pentafluorophenyl group) boric acid is tall and erect, four (pentafluorophenyl group) borate, four (pentafluorophenyl group) boric acid triphenyl phosphorus, four (pentafluorophenyl group) boric acid triethyl coordination silicon salt, four (pentafluorophenyl group) boric acid benzene (diazonium salt), four-(2,3,4,6-tetrafluoro phenyl) boric acid trimethyl ammoniums, four-(2,3,4, 6-tetrafluoro phenyl) boric acid triethyl ammonium, four-(2,3, 4,6-tetrafluoro phenyl) boric acid tripropyl ammonium, four-(2, the fluoro-phenyl of 3,4,6-tetra-) boric acid three (normal-butyl) ammonium, four-(2, 3,4,6-tetrafluoro phenyl) boric acid dimethyl (tertiary butyl) ammonium, four-(2,3,4,6-tetrafluoro phenyl) boric acid DMA salt, four-(2,3,4,6-tetrafluoro phenyl) boric acid N, N-diethylbenzene amine salt, four-(2,3,4,6-tetrafluoro phenyl) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline salt), four-(2,3,4,6-tetrafluoro phenyl) boric acid are tall and erect, four-(2,3,4,6-tetrafluoro phenyl) borate, four-(2,3,4,6-tetrafluoro phenyl) boric acid triphenyl phosphorus, four-(2,3,4,6-tetrafluoro phenyl) boric acid triethyl coordination silicon salt, four-(2,3,4,6-tetrafluoro phenyl) boric acid benzene (diazonium salt), four (two (trifluoromethyl) phenyl of 3,5-) boric acid trimethyl ammonium, four (two (trifluoromethyl) phenyl of 3,5-) boric acid triethyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid tripropyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid three (normal-butyl) ammonium, four (two (trifluoromethyl) phenyl of 3,5-) boric acid three (tertiary butyl) ammonium, DMA salt four (two (trifluoromethyl) phenyl of 3,5-) boric acid, four (two (trifluoromethyl) phenyl of 3,5-) boric acid N, N-diethylbenzene amine salt, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dimethyl-(2, 4, 6-Three methyl Benzene amine salt), four (two (trifluoromethyl) phenyl of 3,5-) boric acid is tall and erect, four (two (trifluoromethyl) phenyl of 3,5-) borate, four (two (trifluoromethyl) phenyl of 3,5-) boric acid triphenyl phosphorus, four (two (trifluoromethyl) phenyl of 3,5-) boric acid triethyl coordination silicon salt, four (two (trifluoromethyl) phenyl of 3,5-) boric acid benzene (diazonium salt), four (pentafluorophenyl group) boric acid two-(sec.-propyl) ammonium, four (pentafluorophenyl group) boric acid dicyclohexyl ammonium, four (pentafluorophenyl group) boric acid three (o-tolyl) phosphorus, four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl) phosphorus, four (perfluorophenyl) borate, 1-(4-(three (pentafluorophenyl group) boric acid)-2,3,5,6-tetrafluoro phenyl) tetramethyleneimine, four (pentafluorophenyl group) boric acid, 4-(three (pentafluorophenyl group) boric acid)-2,3,5,6-ptfe pyridines, four (two (trifluoromethyl) phenyl of 3,5-) boric acid) triphenylcarbenium, with their combination.

A1. the method according to any one of embodiment A-Z, wherein said temperature is about 0 DEG C of-Yue 300 DEG C, and pressure is about 10MPa for about 0.35MPa-, and the time is about 0.1 minute-Yue 24 hours, or their combination.

B1. the method according to any one of embodiment A-A1, wherein said temperature is about 50 DEG C of-Yue 150 DEG C.

C1. the method according to any one of embodiment A-B1, wherein said polymkeric substance comprises the ethene of at least 50 % by mole.

D1. the method according to any one of embodiment A-C1, wherein said polymkeric substance comprises the ethene of at least 75 % by mole.

E1. the method according to any one of embodiment A-D1, wherein said polymkeric substance comprises the ethene of at least 99.9 % by mole.

F1. the method according to any one of embodiment A-E1, wherein said polymkeric substance has:

A) every 1000 at least 0.5, carbon atom polymkeric substance have the side chain of 7 or more carbon atoms;

B) 100 DEG C or higher Tm being measured by DSC;

C) the saturated end of the chain of 1:1-5:1 and the ratio of allyl chain ends;

D) by ¹³c NMR measure at least 50% the ratio of per molecule vinyl;

E) by ¹the Mn of at least 250g/mol that H NMR measures; Or their combination.

G1. the method according to any one of embodiment A-F1, wherein said polymkeric substance has 250g/mol-100, the Mn of 000g/mol.

H1. the method according to any one of embodiment A-G1, wherein said polymkeric substance has the side chain that every 1000 at least 1.0, carbon atom polymkeric substance have 7 or more carbon atoms.

I1. the method according to any one of embodiment A-H1, wherein said polymkeric substance comprises 110 DEG C or higher Tm.

J1. the method according to any one of embodiment A-I1, wherein said polymkeric substance has the 1400ppm aluminium be less than measured by ICPES, the transition metal being less than the 3rd, 4,5 or 6 races of 1400ppm measured by ICPES, or their combination.

K1. the method according to any one of embodiment A-J1, wherein said polymkeric substance has the density being greater than 0.96g/cc.

L1. according to embodiment A-K1, wherein said polymkeric substance has the branch index g' of 0.90 or lower _vis.

M1. the method according to any one of embodiment A-L1, one or more alkene wherein said comprise propylene.

N1. the method according to any one of embodiment A-M1, wherein said polyolefine comprises the propylene of at least 50 % by mole.

O1. polyolefin polymer, has:

A) allyl chain ends of at least 50%; With

B) by ¹the Mn of at least 200g/mol that H NMR measures;

This polymkeric substance is by comprising following method preparation:

One or more alkene are contacted with catalyst system being enough to produce under the temperature of this polyolefin polymer, pressure and time;

Formula I is by following expression:

M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀hydrocarbyl group, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ²⁸in two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, or their combination; With

Y is divalence C ₁-C ₂₀alkyl;

Formula II is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Y is divalence C ₁-C ₂₀hydrocarbyl group, and/or

Wherein produce described polyolefin polymer according to embodiment A-M1.

P1. the polyolefin polymer according to embodiment O1, comprises the ethene of at least 50 % by mole.

Q1. the polyolefin polymer according to any one of embodiment O1-P1, comprises the ethene of at least 75 % by mole.

R1. the polyolefin polymer according to any one of embodiment O1-Q1, comprises the ethene of at least 99.9 % by mole.

S1. the polyolefin polymer according to any one of embodiment O1-R1, has:

B) 100 DEG C or higher Tm being measured by DSC;

C) the saturated end of the chain of 1:1-5:1 and the ratio of allyl chain ends;

D) by ¹³c NMR measure at least 50% the ratio of per molecule vinyl;

E) by ¹the Mn of at least 250g/mol that H NMR measures; Or their combination.

T1. the polyolefin polymer according to any one of embodiment O1-S1, has 250g/mol-100, the Mn of 000g/mol.

U1. the polyolefin polymer according to any one of embodiment O1-T1, has the side chain that every 1000 at least 1.0, carbon atom polymkeric substance have 7 or more carbon atoms.

V1. the polyolefin polymer according to any one of embodiment O1-U1, has 110 DEG C or higher Tm.

W1. the polyolefin polymer described in any one of basis-embodiment O1-V1, comprises the aluminium being less than 1400ppm measured by ICPES, the transition metal being less than the 3rd, 4,5 or 6 races of 1400ppm measured by ICPES, or their combination.

X1. the polyolefin polymer according to any one of embodiment O1-W1, has the density being greater than 0.96g/cc.

Y1. the polyolefin polymer according to any one of embodiment O1-X1, has 0.90 or less branch index g' _vis.

Z1. the polyolefin polymer according to any one of embodiment O1-Y1, comprises propylene.

A2. the polyolefin polymer according to any one of embodiment O1-A2, comprises the propylene of at least 50 % by mole.

Embodiment

Can refer to the discussion before nonrestrictive embodiment further describes.Four kinds of exemplary catalyst compound (A, B, C and D), separately according to one or more above-mentioned embodiments, to be synthesized and some are used to olefin polymerization.Unless otherwise noted, all reactions are under purified nitrogen atmosphere, and use the glove box of standard, high vacuum or Schlenk technology are carried out.The solvent of all uses is anhydrous, deoxidation and according to known step purifying.All parent materials purchased from Aldrich and before the use purifying or prepare according to step well known by persons skilled in the art.

the synthesis of compound A – D:

9-(2-methoxyl group-5-aminomethyl phenyl)-9H-carbazole (1): by bromo-for 2-4-methylanisole (20.11g, 100mmol, 1 equivalent) and carbazole (20.06g, 120mmol, 1.2 equivalents) be dissolved in Isosorbide-5-Nitrae-diox (400mL).With the addition of Tripotassium phosphate (37.15g, 175mmol, 1.75 equivalents), cupric iodide (I) (0.95g, 5mmol, 0.05 equivalent) and racemize anti-form-1,2-diamino-cyclohexane (2.4mL, 20mmol, 0.2 equivalent) and reaction backflow two days.Reaction is cooled to room temperature, is then split by vinyl acetic monomer (200mL) and water (300mL).By vinyl acetic monomer (3x200mL) aqueous layer extracted.The organic layer merged saturated salt solution cleaning, by dried over sodium sulfate, filters, and concentrates under reduced pressure.Resistates, at the upper purifying of silica dioxide gel (150g), is used in 3% vinyl acetic monomer wash-out in heptane to obtain the compound 1 (13.5g, 45% yield) as yellow solid.

2-(9H-carbazole-9-base)-4-methylphenol (2): by the 1.0M Boron tribromide solution (90mL in methylene dichloride, 90mmol, 1.9 equivalents) be dropwise added at-78 DEG C in 30 minutes, compound 1 (13.5g in anhydrous methylene chloride (400mL), 46.98mmol, 1 equivalent) solution.When liquid chromatography mass coupling method (LCMS) represents that reaction completes, reaction is heated to room temperature.Reaction ice-water (200mL) quenching.By layer separately and by methylene dichloride (2x100mL) aqueous phase extracted.The organic layers with sodium sulfate merged is dry, filters, and concentrates under reduced pressure.Resistates is purifying on ANALOGIX 40-150g post, is used in 0-20% vinyl acetic monomer wash-out in heptane to obtain the compound 2 (12.3g, 95% yield) as yellow oil.

6,6'-((ethane-1,2-bis-base two (methyl azane two base)) two (methylene radical)) two (2-(9H-carbazole-9-base)-4-methylphenol) (3): by compound 2 (3.4g, 12.44mmol, 2 equivalents), paraformaldehyde (1.87g, 62.2mmol, 10 equivalents), N, the mixture of N '-dimethyl quadrol (0.67mL, 6.22mmol, 1 equivalent) and dehydrated alcohol (100mL) refluxes 18 hours.Reaction is cooled to room temperature, and then concentrates under reduced pressure.Purifying on resistates ANALOGIX25-60g post, is used in gradient 0-30% vinyl acetic monomer wash-out in heptane to obtain the compound 3 (1.1g, 27% yield) as white solid.

9-(5-fluoro-2-p-methoxy-phenyl)-9H-carbazole (4): by bromo-for 2-4-fluoroanisole (20g, 10mmol, 1 equivalent) and carbazole (18.4g, 11mmol, 1.1 equivalents) be dissolved in Isosorbide-5-Nitrae-diox (200mL).Add potassium sulfate ternary hydrate (46g, 20mmol, 2 equivalents), cupric iodide (I) (1g, 0.5mmol, 0.05 equivalent) and 1,2-diaminopropanes (1mL, 1.3mmol, 0.13 equivalent) and reaction backflow 18 hours.Reaction is cooled to room temperature and passes through diatomite filtration.Filtrate is concentrated and residue purified over silica gel (250g) purifying under reduced pressure, and the gradient 0-10% vinyl acetic monomer be used in heptane obtains the compound 4 (7.6g, 26% yield) as the white solid polluted by carbazole.Use this material subsequently.

2-(9H-carbazole-9-base)-4-fluorophenol (5): at-78 DEG C, by the 1.0M Boron tribromide solution (60mL in methylene dichloride, 60mmol, 3 equivalents) in 30 minutes, be dropwise added into compound 4 (5.8g, 20mmol, 1 equivalent) solution in methylene dichloride (60mL).When ¹when H-NMR Indicator Reaction completes, react and stirred 4 hours at-78 DEG C.Reactant is poured into saturated sodium bicarbonate (100mL) and with 10% sodium hydroxide by pH regulator to 8.By layer separately and by methylene dichloride (3x20mL) aqueous phase extracted.The organic layers with sodium sulfate merged is dry, filters, and concentrates under reduced pressure.Residue purified over silica gel (100g) purifying, is used in the dichloromethane eluent of the gradient 60-100% in heptane.Product containing fraction is merged, concentrated under reduced pressure and in heptane (10mL) 20% methyl tertiary butyl ether in clay into power to obtain the compound 5 (4.3g, 78% yield) as white solid.

6,6'-((ethane-1,2-bis-base two (methyl azane two base)) two (methylene radical)) two (2-(9H-carbazole-9-base)-4-fluorophenol) (6): compound 5 (1.5g, 5.4mmol, 2 equivalents), paraformaldehyde (716mg, 5.4mmol, 2 equivalents), N, N '-dimethyl quadrol (300 μ L, 2.7mmol, 1 equivalent) and the mixture of dehydrated alcohol (20mL) reflux 18 hours (after 2 hours, reaction completes about 60%).Reaction is cooled to room temperature, then concentrates under reduced pressure.Residue purified over silica gel (50g) purifying, is used in the dichloromethane eluent of the gradient 60-100% in heptane to obtain the compound 6 (640mg, 34% yield) as white solid.

2-(9H-carbazole-9-base)-6-(1,3-methylimidazole alkane-2-base) phenol (7): in 100mL round-bottomed flask, 2-(9H-carbazole-9-base) salicylic aldehyde (0.573g, 2.06mmol) is dissolved in the methyl alcohol of 30mL and is heated to 50 DEG C.Quadrol (0.176g, 2.00mmol) is also dissolved in the methyl alcohol of 10mL.When having dissolved all 2-(9H-carbazole-9-base) salicylic aldehyde, add the solution of quadrol lentamente.After two hours, flask is removed and cool overnight from thermal source.Precipitation be collected and without the need to be further purified for next step.

2-(9H-carbazole-9-base)-6-((methyl (2-(methylamino) ethyl) is amino) methyl) phenol (8): stir the slurry 7 from synthesis before in room temperature in 100mL round-bottomed flask.Sodium borohydride (0.640g, 16.9mmol) is added with aliquot in 30 minutes.Observed gas effusion.After three hours, methyl alcohol removes in a vacuum and adds water.The solid produced is filtered and by cold methanol wash.Dry white solid is to produce 8 (0.585g, 79% yields) in a vacuum.

2-(((2-((3-(9H-carbazole-9-base)-2-hydroxybenzyl) (methyl) is amino) ethyl) (methyl)-amino) methyl)-4,6-dibromophenol (9): 8 (0.218g, 0.606mmol) with 2-brooethyl-4,6-dibromophenol (0.209g, 0.606mmol) is dissolved in the THF of 20mL.Triethylamine (1.2mL, 8.61mmol) is added into slightly pinkish red solution.Define white precipitate immediately.Reaction is stirred spend the night, afterwards, removing volatile matter and interpolation methyl alcohol are to prepare slurry.Solid is filtered and drying in a vacuum, creates white solid (0.215g, 57% yield).

[6,6'-((ethane-1,2-bis-base two (methyl azane two base)) two (methylene radical)) two (2-(9H-carbazole-9-base)-4-methylphenol)] dibenzyl zirconium (IV) (A): in nitrogen atmosphere, 3 (107mg, 0.17mmol) of toluene solution (5mL) are added into the ZrBn of yellow toluene solution (5mL) ₄(77mg, 0.17mmol), forms the solution of deep yellow.At room temperature stir after 15 minutes, except desolventizing is to obtain tacky yellowish solid.Product washed with pentane and dry using the compd A (producing 135mg, 88%) obtained as yellow solid in a vacuum.Compd B-D is prepared in the mode being similar to compound 6,9 or 3 and corresponding Group IV tetrabenzyl precursor.

polymerization process:

Vinyl polymerization carries out in parallel pressure reactor, and it is described in U.S. Patent number 6,306,658,6,455,316 and 6,489,168l; WO 00/09255; With the people such as Murphy, J.Am.Chem.Soc., 2003,125,4306-4317, each patent is incorporated to herein by reference.Preweighted vial liner plate and disposable stirring rake are mounted to each reaction vessel of reactor, and it contains 48 independent reaction vessels.Then, reactor be closed and each container by the temperature (75-140 DEG C) that is heated to separately set be forced into the pressure (being generally 0.93MPa (135psi)) of the ethene preset.Then, the methylaluminoxane solution (in toluene 30wt%) adding 500 equivalents serves as promotor/scavenging agent.Then, the content in 800rpm stirred vessel.By the toluene solution of catalyzer (A-D, 0.20mmol/L, 5-20nmol) and then the isohexane (500 μ L) of another decile is added into reactor.Carry out all experiments in quadruplicate.Remain on by conputer controlled the level that in each reaction vessel, ethylene pressure is presetting simultaneously, then make to react and carry out until the time set limits (normally 30 minutes) or until a certain amount of ethene is reacted consumption.At this moment, by being exposed to air, quenching is reacted.After polymerization, the vial containing polymer product and solvent is removed from the glove box of pressure-active element and inert atmosphere, and the GENEVAC HT-12 whizzer operated under being used in the temperature of rising and the pressure of minimizing and GENEVAC VC3000D vacuum-evaporator removing volatile constituent.Have collected the representational polymer samples of each catalyzer under respective polymerizing condition and pass through ¹h and ¹³c NMR spectroscopic analysis to measure character such as Mn, number/1000 carbon of ethyl branch, amount/1000 carbon of long chain branching (LCB) and the number of every polymer chain vinyl ends.

The aggregated data that table 1 shows is intended to the representative of the catalytic property of compound A – D and is not widely.

The high-throughput polymerization result that table 1. is selected

The sign of the polymkeric substance that table 2. is selected

Note:

LCB*=long chain branching is longer than 6 carbon, and all LCB of calculating hypothesis are " Y-type ".

ND=does not determine

As shown in data, catalyst compound disclosed herein, catalyst system and polymerization process provide the new catalyzer with improving and the system for olefinic polymerization, it produces the polymkeric substance of the character with improvement, such as high polymers fusing point, high polymers molecular weight, the transformation efficiency increased and/or comonomer are incorporated to, and it can comprise the long chain branching of significant quantity and/or the ethenyl blocking of significant quantity further.

Catalyzer provides the improvement of catalyst activity in one embodiment, produces the polymkeric substance of the character with improvement, or more both.In one embodiment, crystallographic techniques shows, additional member ring systems or system (such as, carbazole member ring systems) are horizontal orientations, such as, perpendicular to phenol ring.In one embodiment, these catalyzer have such structure, and this structure is that polymer-based carbon part retains and provide wide passage for monomer insertion during polymerization process.Therefore, the catalyzer of a kind of embodiment according to present disclosure provides a kind of ability to control one or more character of being polymerized, tacticity, comonomer insertion etc.

All documents as herein described are incorporated to herein by reference, comprise any priority documents and/or test procedure, reach they and degree consistent herein, but condition is any priority documents does not mention in the initial application submitted to or the document submitted to is not incorporated to herein by reference.As what obviously see from large volume description before and the concrete embodiment of the present invention, although form of the present invention has been illustrated and described, multiple amendment can be made and do not deviated from the spirit and scope of the present invention.Therefore, be not intended to limit the present invention thus.Similarly, in order to the object of Australian Patent method, term " comprises " and is considered to " comprise " synonym with term.Similarly, before composition, key element or one group of key element, there is conjunction " to comprise ", should be understood us and also contemplated identical composition or one group of key element, they have conjunction " substantially by ... composition ", " by ... composition ", " being selected from by ... the group of composition ", or "Yes" is enumerating composition, before one or more key element, and vice versa.

Claims

1. a method, comprising:

A) at least 50% allyl chain ends; With

B) by ¹the Mn of at least 200g/mol that H NMR measures;

Formula I is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ²⁸in two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, or their combination; And

Y is divalence C ₁-C ₂₀alkyl;

Formula II is by following expression:

Wherein M is the transition metal of the 3rd, 4,5 or 6 races;

Y is divalence C ₁-C ₂₀alkyl.

2. method according to claim 1, the R of its Chinese style I ¹-R ²⁸, formula II R ¹-R ²¹, or above-mentioned two or more in both be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings.

3. method according to claim 1, its Chinese style I, formula II, or more both M be Hf, Ti or Zr.

4. method according to claim 1, its Chinese style I, formula II, or more both each X be halogen or C independently ₁-C ₇alkyl.

5. method according to claim 1, its Chinese style I, formula II, or more both each X be benzyl.

6. method according to claim 1, each R of its Chinese style I ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸, formula II each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹, or more be either way hydrogen, halogen or C independently ₁-C ₃₀alkyl.

7. method according to claim 1, wherein said catalyst compound according to formula I, wherein R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸in one or more be methyl, fluorine-based or their combination.

8. method according to claim 1, wherein said catalyst compound is according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹and R ¹⁴for methyl;

R ²-R ¹³and R ¹⁵-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

9. method according to claim 1, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl;

R ², R ³, R ⁵-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

10. method according to claim 1, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹and R ¹⁴for methyl;

R ⁴and R ¹⁷for fluorine-based;

R ², R ³, R ⁵-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸-R ²⁸for hydrogen; With

Y is-CH ₂cH ₂-.

11. methods according to claim 1, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl;

R ⁸, R ¹¹, R ²¹and R ²⁴for the tertiary butyl;

Y is-CH ₂cH ₂-.

12. methods according to claim 1, wherein said catalyst compound according to formula I, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹, R ⁴, R ¹⁴and R ¹⁷for methyl;

R ⁸, R ¹¹, R ²¹and R ²⁴for sym-trimethylbenzene base;

Y is-CH ₂cH ₂-.

13. methods according to claim 1, wherein said catalyst compound according to formula II, wherein R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, and R ²¹in one or more be methyl, bromo, adamantyl or their combination.

14. methods according to claim 1, wherein said catalyst compound according to formula II, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹and R ¹⁴for methyl;

R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen;

R ¹⁷and R ¹⁹for bromine; With

Y is-CH ₂cH ₂-.

15. methods according to claim 1, wherein said catalyst compound according to formula II, wherein,

M is Zr;

X ¹and X ²for benzyl;

R ¹, R ¹⁴and R ¹⁷for methyl;

R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰, and R ²¹for hydrogen;

R ¹⁹for 1-adamantyl; With

Y is-CH ₂cH ₂-.

16. methods according to claim 1, wherein said catalyst compound according to formula II, wherein,

M is Hf;

X ¹and X ²for benzyl;

R ¹and R ¹⁴and R ¹⁷for methyl;

R ²-R ¹³, R ¹⁵, R ¹⁶, R ¹⁸, R ²⁰and R ²¹for hydrogen;

R ¹⁹for 1-adamantyl; With

Y is-CH ₂cH ₂-.

17. methods according to claim 1, its Chinese style I, formula II, above both Y are-CH ₂cH ₂-or 1,2-cyclohexylidene.

18. methods according to claim 1, its Chinese style I, formula II, above both Y are-CH ₂cH ₂cH ₂-.

19. methods according to claim 1, its Chinese style I, formula II, above both Y comprise the C containing connecting base skeleton ₁-C ₄₀bivalent hydrocarbon radical, described connection base skeleton comprises bridging at nitrogen-atoms N ¹and N ²between 1-18 carbon atom.

20. methods according to claim 1, its Chinese style I, formula II, above both Y are for comprising O, S, S (O), S (O) ₂, Si (R ') ₂, P (R '), N, N (R ') or their combination C ₁-C ₄₀bivalent hydrocarbon radical, wherein each R ' is C independently ₁-C ₁₈alkyl.

21. methods according to claim 1, wherein said polymkeric substance has the aluminium being less than 1400ppm measured by ICPES, the 3rd, 4,5 or 6 group 4 transition metals being less than 1400ppm measured by ICPES, or their combination.

22. polyolefin polymers, comprise:

A) at least 50% allyl chain ends; With

B) by ¹the Mn of at least 200g/mol that H NMR measures;

Described polymkeric substance is by comprising following method preparation:

Under being enough to produce polyolefinic temperature, pressure and time, one or more alkene are contacted with catalyst system, comprise:

Formula I is by following expression:

M is the transition metal of the 3rd, 4,5 or 6 races;

Each R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷, and R ²⁸be hydrogen independently, C ₁-C ₄₀alkyl, the functional group of the element of containing element periodictable 13-17 race, or R ¹-R ²⁸in two or more can be joined together to form C independently ₄-C ₆₂the ring structure of ring-type or many rings, or their combination, or their combination; With

Y is divalence C ₁-C ₂₀alkyl;

Formula II is by following expression:

M is the transition metal of the 3rd, 4,5 or 6 races;

Y is divalence C ₁-C ₂₀alkyl.

23. polyolefin polymers according to claim 22, comprise the ethene of at least 50 % by mole.

24. polyolefin polymers according to claim 22, have:

B) 100 DEG C or higher Tm being measured by DSC;

C) the saturated end of the chain of 1:1-5:1 and the ratio of allyl chain ends;

D) by ¹³c NMR measure at least 50% the ratio of per molecule vinyl;

E) by ¹the Mn of at least 250g/mol that H NMR measures;

Or their combination.

25. polyolefin polymers according to claim 22, comprise 250g/mol-100, the Mn of 000g/mol.

26. polyolefin polymers according to claim 22, have the side chain that every 1000 at least 1.0, carbon atom polymkeric substance have 7 or more carbon atoms.

27. polyolefin polymers according to claim 22, have 110 DEG C or higher Tm.

28. polyolefin polymers according to claim 22, comprise the aluminium being less than 1400ppm measured by ICPES, the transition metal being less than the 3rd, 4,5 or 6 races of 1400ppm measured by ICPES, or their combination.

29. polyolefin polymers according to claim 22, have the density being greater than 0.96g/cc.

30. polyolefin polymers according to claim 22, have the branch index g' of 0.90 or less _vis.

31. polyolefin polymers according to claim 22, comprise propylene.